CN100564411C - (methyl) acrylic acid polymer and unsaturated alkylene glycol copolymer and production method thereof - Google Patents

(methyl) acrylic acid polymer and unsaturated alkylene glycol copolymer and production method thereof Download PDF

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CN100564411C
CN100564411C CNB2006100956538A CN200610095653A CN100564411C CN 100564411 C CN100564411 C CN 100564411C CN B2006100956538 A CNB2006100956538 A CN B2006100956538A CN 200610095653 A CN200610095653 A CN 200610095653A CN 100564411 C CN100564411 C CN 100564411C
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CN1896111A (en
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米田淳郎
津守隆弘
藤井义一
山口繁
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Nippon Shokubai Co Ltd
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Abstract

The present invention relates to (methyl) acrylic acid polymer, wherein represent the S value of the element sulphur amount of introducing to be not less than 35, it defines by following formula, S=(contained quantity of S in the polymkeric substance)/(total quantity of S) * 100.Should (methyl) acrylic acid polymer be to have low-molecular-weight water-soluble polymers, it only has little foreign matter content, is not settled out impurity during low tempertaure storage, and dispersed, sequestering power and antigelation performance excellence.

Description

(methyl) acrylic acid polymer and unsaturated alkylene glycol copolymer and production method thereof
The application is dividing an application of an application for a patent for invention, and the applying date of its female case is that October 3, application number in 2002 are 02154505.7, denomination of invention is " (methyl) acrylic acid polymer and unsaturated alkylene glycol copolymer and a production method thereof ".
Technical field
The present invention relates to be advantageously used in following application scenario, as water type dispersion agent, (methyl) acrylic acid polymer of washing agent and washing builder, its a kind of production method, and the washing composition of this polymkeric substance of use.
The invention still further relates to and can be advantageously used in following application scenario, as water type dispersion agent, washing agent, the unsaturated alkylene glycol copolymer of cement additire and washing builder, its a kind of production method, and the washing composition of this polymkeric substance of use.
Background technology
(about the prior art of (methyl) acrylic acid polymer)
For water miscible polymkeric substance, as have low-molecular-weight polyacrylic acid and polymaleic acid, be advantageously used in the dispersion agent of mineral dye and metal ion in the past, washing agent and washing builder.As a kind of method that obtains such low-molecular weight water-soluble polymer, known have, and for example, is disclosed in the method among JP-A-64-38403 and the JP-A-05-86125.
Be disclosed in the method among the JP-A-64-38403, be with water-soluble azo-type radical polymerization initiator one or more water-soluble vinyl monomers (vinyl monomer) to be carried out radical polymerization, the amount that is expected at the sulfonium ion of introducing in the reactive system is the 0.1-30mol% based on amount of monomer.Monomer used herein has no particular limits, and only needing it is water miscible vinyl monomer.Use this method can obtain molecular weight and be not less than tens thousand of low-molecular-weight water-soluble polymerss, and the circulation ratio of method is satisfactory.
JP-A-05-86125 can obtain forming the vinylformic acid that is no less than 95mol% or the water-soluble polymers of acrylate, and it is finished by vinylformic acid or acrylate are carried out aqueous solution polymerization when keeping pH value of solution to be 6-9 (under the neutrallty condition).At this moment, the number-average molecular weight of polymkeric substance is 300-10000, and dispersity is 1.3-2.3.Because this method gained water-soluble polymers has the dispersity (having narrow molecular weight distribution) of lower molecular weight and close limit, it shows the dispersing property of height and is advantageously used in various dispersion agents and detergent builder.
JP-B-60-24806 discloses a kind of method of producing the acrylate type low-molecular weight polymer.The method of JP-B-60-24806 is a kind of acrylic acid an alkali metal salt with (A), (B) acrylamide or 2-hydroxyethyl (methyl) acrylate and (C) can with above-mentioned (A) (B) hydrophilic monomer of component copolymerization, carry out aqueous solution polymerization with the ratio of regulation.Polymerizing condition is that every mole of component (A) is no less than 10 litres of air, and polymerization temperature is not higher than 80 ℃.
This method gained acrylate type water-soluble polymers molecular weight ranges is 500-100000, and narrow molecular weight distribution.And this water-soluble polymers is carried impurity hardly secretly and is only produced slight adding lustre to.Also have, the terminal of the straight or branched of every mole of this water-soluble polymers can be introduced the 0.5-1.5 sulfenyl.Thus, this water-soluble polymers is superior aspect dispersed and chelating ability, can be advantageously used in the dispersion agent of mineral dye, detergent builder, sanitising agent, and washing agent.
As the technology of producing the low-molecular weight polymer is not above-mentioned water-soluble polymers, can quote and be disclosed in US3, the method in 646,099.The low-molecular weight polymer that is disclosed in this publication is intended as the electric conductivity coating material.It is formed at the polymerization of (methyl) vinyl cyanide and a kind of hydrophobic monomer, and need satisfy the hydrophobic monomer ratio and be not less than this basic demand of 40mol%.According to this method, can produce molecular weight and not be higher than 25000 polymkeric substance.
But,, be difficult on the end group of related polymer or main chain, quantitatively introduce sulfenyl by the technology that is disclosed among JP-A-64-38403 and the JP-A-05-86125.Thus, by these technology gained water-soluble polymerss, its dispersiveness and resistant to gelling be can not be counted as outstanding, and are not dispersion agents, detergent builder, the optimal selection of sanitising agent and washing agent.
By the technology that is disclosed among the JP-B-60-24806, can wherein be had the water-soluble polymers that sulfenyl is to a certain degree introduced.Because the used monomer of this technology is acrylate (an alkali metal salt), polymerization reaction system is neutral basically fully.
The polymerization of carrying out under the neutrallty condition of such use acrylate, when the solid constituent concentration in the reactive system increased, the viscosity of reaction soln was tending towards significantly increasing with polymerisation run, thereby the molecular weight of product polymkeric substance is improved to a great extent.Thus, the technology of instructing among the JP-B-60-24806 when being used for monomer polymerization, having under the high density condition and can't produce low-molecular weight polymer, thus the shortcoming that production efficiency is reduced.
Simultaneously, by US3, the technology in 646,099 can advantageously be produced low-molecular weight polymer.But, US3, the Technology Need usage ratio in 646,099 is no less than the hydrophobic monomer of 40mo1% and produces polymkeric substance.The gained low-molecular weight polymer is water insoluble thus.Especially, US3, the technical purpose in 646,099 is to produce the low-molecular weight polymer as the electric conductivity coating material.By simply monomer being replaced with water-soluble monomer, can not produce satisfied water-soluble polymers.
For the above-mentioned dispersion agent that is advantageously used in, the water-soluble low molecular weight polymkeric substance of washing agent and washing builder, water-soluble polymers is except that dispersing property and calcium-binding ability (it is intrinsic by water-soluble polymers), excellent antigelation performance preferably should be arranged, that is, and antigellant quality.But disclosed method in the above publication can not be produced the water-soluble polymers with excellent anti gelling property.Thus, they can not obtain fully satisfying dispersion agent, the water-soluble polymers that washing agent and washing builder require.
Therefore, aforesaid method can not satisfy the requirement of the low-molecular-weight water-soluble polymers with excellent dispersity and anti-chelating ability and antigelation performance excellence fully, thereby can not satisfy the requirement of making effective water-soluble polymers product fully.
The inventor finds to have lower molecular weight, (methyl) acrylic acid polymer of dispersing property and chelating ability, antigelation performance excellence, can be effectively by under acidic conditions, will have quantitatively the sulfenyl of introducing at end group and contain (methyl) acrylic acid monomer and carry out polymerization and prepare.The synthetic method of above-mentioned (methyl) acrylic acid polymer is: with 50-100mol% (methyl) vinylformic acid and 0-50mol% water miscible can with monoene key (monoethylenically) unsaturated monomer polymerization in the aqueous solution of (methyl) acrylic acid copolymer, and its end group is connected with sulfenyl.This (methyl) acrylic acid polymer is characterised in that the Q value of representing the antigelation performance, and it is defined by following formula: Q=degree of gelation * 10 5/ weight-average molecular weight is lower than 2.0.Should (methyl) acrylic acid polymer be have low-molecular-weight, the water-soluble polymers of resistant to gelling and dispersed and chelating excellence.In producing the method for this polymkeric substance, the usage ratio that contains (methyl) the acrylic acid hydrophilic monomer that is not less than 50mol% is not less than 60mol%, and the pH of system that carries out monomer polymerization is less than 5, and degree of neutralization is less than 40mol%.Initiator is used in above-mentioned monomeric polymerization, and it is respectively the combination of the material of persulphate and bisulfite for one or more.More preferably, the usage ratio that contains (methyl) the acrylic acid hydrophilic monomer that is not less than 50mol% is not less than 60mol%, and this monomer dropwise adds and carries out polymerization, be aggregated in PH less than carrying out under 5 the acidic conditions, degree of neutralization is less than 40mol%, paradigmatic system is set in the level that is not less than 40 weight % dropwise adding the solids concn of monomeric process when finishing, and weight-average molecular weight is set in the level of 3000-15000.The inventor finds after polymerization, can produce water-soluble low molecular weight, the polymkeric substance of resistant to gelling and dispersed and chelating excellence effectively.This knowledge is set forth in JP-A-11-315115.
Water-soluble polymers among the JP-A-11-315115 is owing to have the dispersion agent of being suitable for, and the performance of washing agent and washing composition synergistic agent has extensive use and be found.
(about the prior art of unsaturated alkylene glycol copolymer)
The multipolymer that known use unsaturated polyalkylene glycol type monomer forms can be used as the synergistic agent of liquid washing agent.For example, as a class unsaturated polyalkylene glycol type monomer of the affixture of oxyethane and 3-methyl-3-butene-1-alcohol and as the monomeric multipolymer of (methyl) acrylic acid class unsaturated monocarboxylic type can be used as the synergistic agent of liquid washing agent.As the method that obtains such multipolymer, for example, the method that is disclosed among the JP-A-2002-60785 is known.
Disclosed method in the above publication, be mainly to contain a kind of unsaturated monocarboxylic type monomer, or unsaturated pair of carboxylic acid type monomer and the monomeric monomer component copolymerization of a kind of unsaturated polyalkylene glycol type, when using persulphate or hydrogen peroxide, can produce enough polymerizations as initiator.When using this method, it is high to tens thousand of multipolymers to obtain molecular weight, and has good circulation ratio.
The consistency excellence of this method resulting polymers and liquid washing agent, and excellent dispersion, and can be advantageously used for detergent builder, particularly liquid washing agent builder.
As the technology of production lower molecular weight (methyl) acrylic acid polymer (it is not to contain the unsaturated polyalkylene glycol type polymer of monomers), citable is the method that is disclosed among the JP-A-11-315115.
When using in the above-mentioned publication disclosed method, if when mainly containing the monomeric monomer composition of (methyl) acrylic type and being aggregated, use persulphate or bisulfite can make and be aggregated in that (concentration is not less than 40 weight %) is achieved under the high density as initiator.Use this method, can obtain molecular weight and not be higher than tens thousand of low-molecular weight polymers, and have high repeatability.
Have narrow molecular weight distribution by this method resulting polymers, and only produce slight adding lustre to thus.And this polymkeric substance has quantitatively been introduced rhodanine on the end group of its straight or branched.Therefore, this polymer dispersed and resistant to gelling excellence, and help being used for the dispersion agent of mineral dye, washing composition synergistic agent, sanitising agent, and washing agent.
But when the technology among the JP-A-2002-60785 of being disclosed in by use was produced a kind of (methyl) Acrylic Acid Monomer and the monomeric multipolymer of a kind of unsaturated polyalkylene glycol type, its molecular weight just can increase when removing non-polymeric concentration and being lower than the grade of 20 weight %.Polymeric solution may be submitted to gelation.Thus, must sacrifice output to reduce polymerization concentration.In addition, resulting polymers aqueous solution tone deterioration subsequently.Because above-mentioned factor, this polymkeric substance is not the optimal selection as the washing composition synergistic agent.
In addition, by using the method among the JP-A-11-315115, can under high density, produce low-molecular weight polymer.Because this technology mainly is to be used for producing polymkeric substance by (methyl) acrylic type monomer, so low by the consistency of this technology resulting polymers and liquid washing agent.Therefore, by using the method among the JP-A-11-315115 to be difficult to produce the polymkeric substance that is applicable to the liquid washing agent synergistic agent.
By these conventional arts, never may be under high density produce and have lower molecular weight with gratifying efficient, tone, with the polymkeric substance of liquid washing agent consistency, dispersiveness and antigelation performance excellence.
(about the problem of (methyl) acrylic acid polymer)
The inventor resentful to the development of this new technology, further studies (methyl) acrylic acid polymer and the production method thereof that are disclosed among the JP-A-11-315115.Find that (1) produces a large amount of sulfurous gas in process of production as the bisulfite that initiator uses thereafter, the sulfurous gas that produces is dissolved in the liquid phase and forms impurity, the sulfurous gas that breaks away from liquid solution is discharged from system in a large number, the discharging of this sulfurous gas has brought new problem again, promptly to the demand of costly processing, this processing comprises with suitable absorption agent reclaims these obnoxious flavoures and abandoning absorption agent, and (2) are owing to overflow with the form of sulfurous gas as the bisulfite of initiator, and efficient is reduced, the polymerizable molecular amount does not reduce, total add-on of initiator needs to increase, will bring more impurity in the product, the acrylic acid inherent excellent properties of (methyl) produced fails to obtain gratifying abundant displaying, reaches the new problem that produces contamination precipitation in the low tempertaure storage process but also brought quality to descend.
Therefore, an object of the present invention is to provide a kind of (methyl) acrylic acid polymer, it is a kind of have excellent dispersiveness, sequestering power and low-molecular-weight water-soluble polymers of antigelation performance.(methyl) of the present invention acrylic acid polymer can reduce foreign matter content significantly and and then improve its performance.And, (methyl) of the present invention acrylic acid polymer has the high-performance that makes in the production process to be given and keeps stable outstanding performance of preserving down not influenced by storage environment, and reduced by quality or the low tempertaure storage process in produce the problem of contamination precipitation.
Another object of the present invention provides the method for a kind of production (methyl) acrylic acid polymer, and this polymkeric substance is water miscible polymkeric substance, has lower molecular weight, dispersiveness, sequestering power and antigelation performance excellence.By the method for production of the present invention (methyl) acrylic acid polymer, the performance that can in producing (methyl) acrylic acid polymer process, avoid producing in a large number sulfurous gas and consequent impurity and can be further enhanced.
Another object of the present invention provides a kind of washing composition, and (as the high-performance detergent builder) is a kind of to have a lower molecular weight by using for it, and water-soluble (methyl) acrylic acid polymer of dispersed, sequestering power and antigelation performance excellence makes.Washing composition of the present invention has obtained further augmented performance and quality.And washing composition of the present invention has high shelf-stable performance, and it can be not influenced because of storage environment.
(about the problem of undersaturated alkylene glycol copolymer)
Among the JP-A-2002-60785 disclosed undersaturated alkylene glycol copolymer really with the liquid washing agent consistency and dispersed aspect excellent performance, but also expose the deficiency of tone and productivity aspect.Simultaneously, polymkeric substance and the liquid washing agent consistency that is disclosed among the JP-A-11-315115 is poor.Thus, problem solved by the invention is to provide a kind of liquid washing agent level builder, a kind of cement additire and a kind of washing composition that contains with the liquid washing agent level builder of liquid washing agent consistency, dispersiveness and tone aspect excellent performance.
In addition, the present invention's purpose that will realize is to provide a kind of method that polymerize the undersaturated alkylene glycol copolymer of excellent performance aspect liquid washing agent consistency, dispersiveness and tone under high density with high productivity.
Summary of the invention
The inventor is for reaching purpose mentioned above, and at lower molecular weight, (methyl) acrylic acid polymer and the production method thereof of dispersiveness, sequestering power and antigelation performance excellence have been carried out deep research.Thus, they find that it can not show its inherent excellent properties satisfactorily fully when (methyl) acrylic acid polymer really is a kind of water-soluble low molecular weight polymkeric substance that combines dispersiveness, sequestering power and antigelation performance.As if they also find can to reduce the discharging of sulfurous gas and reduce impurity by the consumption (the preferred degree of neutralization that further reduces in the polymerization process) that reduces initiator by prolonging polymerization process (this has reduced productivity) at low temperatures.The result is, can obviously improve (methyl) performance that acrylic acid polymer had, further contamination precipitation in the decline of inhibition quality and the low tempertaure storage process can make the fine quality of the product of giving in the production process not keep permanent stable (promptly can fully show its inherent quality is not lowered) because of the storage environment influence simultaneously.The present invention is based on above-mentioned knowledge is able to perfect.
The inventor finds that also a kind of monomeric monomer of undersaturated polyalkylene glycol type that will contain carries out the polymeric method, promptly by rhodanine is introduced its end group with the high density that is not less than 40 weight %.By this method, can produce the aqueous solution of undersaturated alkylene glycol copolymer and this multipolymer efficiently, this multipolymer have lower molecular weight and with liquid washing agent consistency, dispersiveness, sequestering power and antigelation performance excellence.Based on above-mentioned knowledge, the present invention that they are finally perfect.
First aspect of the present invention is at a kind of (methyl) acrylic acid polymer, the amount of the element sulphur introduced of S value representation wherein, and it defines with following formula: S=(content of S in the polymkeric substance)/(total amount of S) * 100, this value is not less than 35.
Second aspect of the present invention is the production method at a kind of (methyl) acrylic acid polymer, it is characterized in that using a kind of initiator, it is the combination corresponding to one or more materials of persulphate and bisulfite, wherein the bisulfite usage ratio is as 1 o'clock with persulphate, its mass ratio is 0.5-5, the total amount that adds the persulphate of polymerization reaction system and bisulfite should be in every mole of 2-20g treats the monomeric scope of polymeric, and polymerization temperature is in the 25-99 ℃ of scope.
The 3rd aspect of the present invention is at a kind of undersaturated alkylene glycol copolymer, wherein this multipolymer is by (methyl) acrylic type monomer A and the copolymerization of undersaturated polyalkylene glycol type monomers B are made, this multipolymer has rhodanine on its end group, and the S value of the amount of the element sulphur that representative is introduced, it defines with following formula: S=(content of S in the polymkeric substance)/(total amount of S) * 100 is not less than 3.
The 4th aspect of the present invention is the production method at a kind of undersaturated alkylene glycol copolymer, it is by making (methyl) acrylic type monomer A and the copolymerization of undersaturated polyalkylene glycol type monomers B, wherein is used as initiator with the combination corresponding to one or more materials of persulphate and bisulfite.
Specific embodiments
Above-mentioned and other purpose of the present invention, characteristics and advantage will be apparent by the description of following preferred embodiment.
Now, embodiment of the present invention will describe in detail hereinafter.
First aspect of the present invention is at a kind of (methyl) acrylic acid polymer, the amount of the element sulphur introduced of S value representation wherein, and it defines with following formula: S=(content of S in the polymkeric substance)/(total amount of S) * 100, this value is not less than 35.Preferably, this polymkeric substance will be by containing can making with the monomer polymerization of (methyl) vinylformic acid water-soluble monoethylenically unsaturated monomer of copolymerization in the aqueous solution of 50-100mol% (methyl) vinylformic acid and 0-50mol%.In addition, for (methyl) acrylic acid polymer, it contains sulfur-containing group with the sulfonic form that is connected to its end group, and the Q value of its antigelation performance is not less than 3.0, and this value defined is Q=degree of gelation * 10 5/ weight-average molecular weight, the S value of the sulfur-bearing amount of element that representative is introduced preferably is not less than 35.The inventor has found to make (methyl) acrylic acid polymer to have lower molecular weight and dispersiveness, sequestering power and antigelation performance excellence, S value with the amount that obtains the element sulphur that representative introduced is not less than 35 purpose, can finish by the polymerization temperature in the production process and degree of neutralization are controlled in the specialized range.By this control, can suppress the generation of sulfurous gas in a large number and and then suppress the generation of impurity.The S value that obtains the element sulphur amount of introducing by above-mentioned production process and allowing then is not less than 35 polymkeric substance and has especially little foreign matter content.Also can suppress to an extremely low level simultaneously quality is reduced.With polymkeric substance with aqueous solution form at low temperatures the contamination precipitation in the storage process also can be suppressed to an extremely low level.That the polymkeric substance of discussing is better than being proposed by the inventor aspect calcium-binding capacity and be disclosed in (methyl) acrylic acid polymer among the JP-A-11-315115.This polymkeric substance is water white transparency and compares the tone excellence with tradition (methyl) acrylic acid polymer aqueous solution.Therefore, the present invention further improves quality.
For (methyl) acrylic acid polymer, represent the S value of the amount of the element sulphur of introducing usually to surpass 35 and preferably fall into 35-70, more preferably in the scope of 40-60.If represent the S value of the amount of the element sulphur of introducing to be lower than 35, the disadvantage that lacks of sulphur is to make the amount of the required initiator of polymerization to reduce satisfactorily, and then the purpose that makes the generation that effectively suppresses impurity and sulfurous gas generate is difficult to realize, quality is descended and is settled out impurity when low tempertaure storage.Represent the upper limit of S value of the amount of the element sulphur of introducing not need to limit especially.
Along band explanation, " in the polymkeric substance contained S amount " this statement is meant the amount of S as employed in the S value of the amount of the element sulphur of introducing of preamble definition, and it is included in (methyl) acrylic acid polymer.More particularly, this statement refers to be contained in the amount of the S in the macromole component of formation (methyl) acrylic acid polymer, this polymkeric substance is after low molecule component is removed from polymerization gained (methyl) the acrylic acid polymer aqueous solution as impurity and initiator relic, and remain after being conditioned solid constituent content, it uses dialysis process to measure, and describes in detail among the embodiment that quotes hereinafter.In other words, this statement can be regarded as, and refers to be incorporated into the form of a kind of like this sulfur-containing group of sulfonic group the amount of the end group or the S on the side chain of (methyl) acrylic acid polymer.Thus, can infer relievedly, advantageously be introduced into the ratio of the amount that is contained in the S component in the initial used initiator in the polymkeric substance, increase, correspondingly represent the S value of the amount of the element sulphur of introducing to increase with polyreaction.Used term " total amount of S " in the S value defined of the amount of the element sulphur that expression is introduced, refer to (methyl) acrylic acid polymer place mutually in contain the total amount of S.Do not use polymerization raw materials used in S amount and use the total amount of S to be because do not appear in (methyl) acrylic acid polymer (aqueous solution) with the amount of the S (sulphur component) of the form effusion system of sulfurous gas, so can not in the low tempertaure storage process, be precipitated out with the form of sulfur-containing impurities.
Term used herein " (methyl) acrylic acid polymer " refers to a comprehensive notion, it has contained the aqueous solution that contains (methyl) acrylic acid polymer that obtains by polymerization, above-mentioned to wherein having added or from wherein having shifted out solvent to regulate the aqueous solution of solid constituent concentration resemble water, by removing the water solvent in the aqueous solution and the solid matter of dried residue gained, the aqueous solution of (methyl) acrylic acid polymer by suitably removing impurity in the aqueous solution that contains (methyl) acrylic acid polymer that derives from polyreaction and purifying residue gained, to wherein having added or from wherein having shifted out water solvent to regulate the aqueous solution of solid constituent concentration, be dried to solid-state (methyl) acrylic acid polymer, and randomly contain the aqueous solution of following suitable additive, for example, shelf-stable agent (UV light absorber and oxidation inhibitor), tinting material, static inhibitor, along lubrication prescription, weighting agent, fire retardant, and whipping agent, the ratio of its introducing amount is not enough to influence unfriendly the quality of polymerization gained (methyl) acrylic acid polymer.In brief, (methyl) acrylic acid polymer do not need according to shape and composition distinguish especially and only needs contain (methyl) acrylic acid polymer.Thereby (methyl) of the present invention acrylic acid polymer has comprised the situation that only generates the such polymkeric substance of pure (methyl) acrylic acid polymer.Therefore, (methyl) of the present invention acrylic acid polymer only need satisfy element sulphur that representative is introduced above amount the S value requirement and should in the widest as far as possible scope, be understood and be not limited to its title itself.It should straitly not understood (restriction) and is solid constituent or its aqueous solution of (methyl) acrylic acid polymer.From simplifying the angle of production process, recommendable is directly the aqueous solution that comprises (methyl) acrylic acid polymer that derives from polyreaction to be used as, for example, and dispersion agent, washing agent, and detergent builder.From reducing the angle of transportation cost, recommendable is polymkeric substance can be transported with the form of the form of solid matter rather than the bulky aqueous solution, and randomly, when polymkeric substance is used as, for example, dispersion agent, washing agent, when synthesizing, this solid matter is converted into the aqueous solution with detergent builder.From making constant product quality and making the angle of the shelf-stable of product, recommendable is that the aqueous solution that comprises (methyl) acrylic acid polymer that can will derive from polyreaction by removing the impurity in the aqueous solution is converted into the finished product.Thus, polymkeric substance can suitably be given such shape and composition for being fit to different purposes.Promptly, (methyl) acrylic acid polymer does not need to distinguish especially according to shape and composition, and the S value that only needs to satisfy the amount of the element sulphur of being measured with method (describing especially among the embodiment hereinafter) analysis of regulation that representative is introduced by the polymkeric substance that polymerization obtained is not less than 35.
(methyl) of the present invention acrylic acid polymer also should satisfy the requirement to R except that the requirement of the S value of the amount that satisfies element sulphur that above-mentioned representative is introduced, R is defined by following formula: R=(2.3-4.3ppm signal integration ratio)/(the 0.8-2.3ppm integration ratio that comprises the PSA signal) * 100, 1In the HMR spectrum, R value scope should be 1-10.The result is, can be equal to or be better than the effect that gained is operated in the requirement of the S value of the amount by satisfying element sulphur that above-mentioned representative is introduced.That is, (methyl) acrylic acid polymer that satisfies these requirements has extremely low foreign matter content, and its quality that causes because of impurity reduces the to the utmost point low level that is suppressed.In addition, (methyl) like this acrylic acid polymer, the contamination precipitation when it is stored with aqueous solution form at low temperatures is suppressed to the utmost point low level.And, such (methyl) acrylic acid polymer antigelation performance excellence, and calcium-binding capacity is excellent and have an excellent tone.Therefore, further improve the quality and be achieved.
The R value of (methyl) acrylic acid polymer is usually in the scope of 1-15, preferably in the scope of 2-12, more preferably in the scope of 3-10.If should be worth R less than 1, the disadvantage of this reduction is to make resistant to gelling to reduce, it is with respect to the amount that comes from the peak of the amount of contained S in (methyl) acrylic acid polymer, exceedingly increased the total amount (most such peaks come from the impurity as initiator relic one class) at the peak that comes from the organic substance in (methyl) acrylic acid polymer, this makes and is difficult to combine with (methyl) acrylic type multipolymer as sulfonic sulfur-containing group, and then the reduction quality, and may not fully show satisfactorily polymkeric substance is suppressed this effect of contamination precipitation when the low tempertaure storage with aqueous solution form.On the contrary, if above-mentioned R value is higher than 15, the disadvantage of this raising is excessively to have reduced molecular weight and has also reduced the quantity of carboxylic acid and reduced sequestering power.
Here, 2.3-4.3ppm signal integration ratio comprises the peak that comes from mainly the amount that is contained in the S in (methyl) acrylic acid polymer.Simultaneously, the 0.8-4.3ppm integration ratio that comprises the PSA signal comprises that all come from the peak of the organic substance in (methyl) acrylic acid polymer.Prefix abbreviation used herein " PSA " refers to sodium polyacrylate. 1The target sample of HMR spectrum refers to the aqueous solution that contains (methyl) acrylic acid polymer that is used to analyze.Especially, 1The preparation method of the target sample of HMR spectrum is specified in hereinafter among the embodiment, is about to given (methyl) acrylic acid polymer of 1 gram polymerization gained and carries out vacuum-drying to wherein residual solvent component and remove fully.
Then, (methyl) of the present invention acrylic acid polymer need satisfy the requirement of concentration of heavy metal ion scope in the 0.5-10ppm scope, and satisfies the S value of the amount of element sulphur that above-mentioned representative is introduced, and the requirement of preferred R value.The result is to make the peroxide breakdown of using in the polymerization process also reduce the initiator (superoxide) that is comprised in (decomposition) (methyl) acrylic acid polymer and improve tone (colourless and transparent).
Herein, the concentration of heavy metal ion of (methyl) acrylic acid polymer is usually in the 0.05-10ppm scope, preferably in the 0.1-8ppm scope, more preferably in the 0.15-5ppm scope.If concentration of heavy metal ion is lower than 0.05ppm, the disadvantage of this low value is to obtain above-mentioned effect, make initiator (superoxide) amount to reduce with being entirely satisfactory, make when (methyl) acrylic acid polymer is used for the occasion of the excellent tone of needs need with may be contained in (methyl) acrylic acid polymer as the impurity decomposition of initiator or remove, thereby produce extra-pay for purifying.This low value when initiator (superoxide) need be present in (methyl) acrylic acid polymer with bigger amount, may cause safety problem (skin irritation), and this depends on purposes and is similarly purifying and need removing impurity.On the contrary, if concentration of heavy metal ion is higher than 10ppm, although the impurity as initiator that is contained in (methyl) acrylic acid polymer can be decomposed or remove fully satisfactorily, it still may make polymer gel, and, because the adding lustre to of heavy metal ion, be restricted when making this polymkeric substance be used for the occasion of the excellent tone of requirement.
Above-mentioned heavy metal ion does not need to do special restriction.As the concrete example of heavy metal ion, specifiable have iron ion, nickel ion, a chromium ion, and molybdenum ion.Because security is outstanding, the more favourable and iron ion particularly advantageous of iron ion and nickel ion.For adding in the polymkeric substance, this type of heavy metal ion can begin preceding or polyreaction begins the back drawing-in system in polyreaction.The heavy metal ion of liquate can add in the polymkeric substance according to aforementioned ionic concn in the device that uses from a production process.
Along the band explanation, this heavy metal ion does not need chemically or physically as a part and its binding of (methyl) acrylic acid polymer, gets final product and only need appear in (methyl) acrylic acid polymer.
Then, the present invention's (methyl) acrylic acid polymer preferably should satisfy the Q value and be lower than 3.0 requirement, and this value defined is Q=degree of gelation * 10 5/ weight-average molecular weight, and satisfy the S value of the amount of element sulphur that above-mentioned representative is introduced, and the requirement of preferred R value or iron concentration.So far, this polymkeric substance that has the antigelation performance has at other and has low especially molecular weight in low-molecular-weight polymkeric substance usually.For making this polymkeric substance obtain satisfied antigelation performance, need further to reduce the molecular weight that this script has had low-molecular-weight polymkeric substance.But, for having low-molecular-weight polymkeric substance, on the end group of polymkeric substance or side chain with the sulfonium ion form quantitatively thiylation group be difficult, in the time of particularly will making its amount satisfy the S value of the amount of representing the element sulphur of introducing defined above.Therefore, this polymkeric substance can not show its dispersed and detergent power with being entirely satisfactory and can not be advantageously used for dispersion agent, washing agent, or detergent builder.In contrast, introduced sulfur-containing group quantitatively on the end group of the polymkeric substance of (methyl) of the present invention acrylic acid polymer or the main chain.Particularly point out, introducing amount of the sulfur-containing group that it is introduced with the sulfonic group form has satisfied the S value of the amount of the element sulphur that above defined representative introduced.The result is, (methyl) acrylic acid polymer can show excellent antigelation performance, although it requires macromolecule with the traditional polymer phase ratio with antigelation performance.Promptly, when above-mentioned S value is satisfied, and when the Q value of representing the antigelation performance also is limited in the above-mentioned restricted portion, when (methyl) acrylic acid polymer is used as water dispersant, washing agent, or during detergent builder, can resist gelation and performance satisfied especially antigelation ability and calcium-binding ability.Therefore, it can be advantageously used in water dispersant, washing agent, or purposes such as detergent builder.Especially can under use occasion and under storage environment even when mixing (chemical combination), resist gelation owing to this polymkeric substance, so the finished product of this polymkeric substance can demonstrate the quality and the quality stability of further raising with other components.
, represent the Q value of antigelation performance to be usually less than 3.0 herein, preferably be lower than 2.7, more preferably less than 2.5.If this Q value is higher than 3.0, this high value may make the application of the finished product owing to the antigelation scarce capacity is restricted.Along the band explanation, the lower limit of Q value does not need to do special restriction.
In the low-molecular-weight water-soluble polymers process of producing traditional performance antigelation performance, add the amount of demand when producing high molecular weight polymers more of the initiator of polymerization reaction system.By (methyl) acrylic acid polymer that in JP-A-11-315115, proposes before the inventor,, can suppress the increase that this joins the amount of the initiator in the polymerization reaction system owing to have relatively large molecular weight.Therefore, (methyl) like this acrylic acid polymer is compared with the water-soluble polymers of traditional performance antigelation performance and is had tangible cost advantage.Prerequisite is compared for (methyl) acrylic acid polymer among the JP-A-11-315115 with it, and it is identical and reduced (methyl) acrylic acid polymer of initiator amount that the present invention can generate the Q value of antigelation performance.Therefore, this polymkeric substance can further reduce the amount of the impurity that produces owing to initiator and make quality that further raising be arranged.And, cost is further reduced.
Here, the antigelation performance is calculated with the Q value of representing the antigelation ability and is carried out classification according to calculation result.Represent the calculating of the Q value of antigelation ability to be based on following formula, be to use degree of gelation and the weight-average molecular weight of (methyl) acrylic acid polymer to calculate.
Q=degree of gelation * 10 5/ weight-average molecular weight
Give " degree of gelation " in the following formula for measuring, can advantageously use the currently known methods of the degree of gelation of mensuration (methyl) acrylic acid polymer.Specifically, low concentration aqueous solution's (it for example has the solid constituent concentration of 1 weight %) by in buffered soln, adding (methyl) of the present invention acrylic acid polymer and calcium chloride water and it is mixed prepare test soln.By making test soln under specified temperature, keep the specified time (for example, 90 ℃ and 1 hour), measure its specific absorption at UV-light (UV) wavelength zone thereafter, can measure the degree of gelation of (methyl) acrylic acid polymer.Specifically describe among the embodiment that the method for mensuration degree of gelation will be quoted from hereinafter.
Then, the weight-average molecular weight of (methyl) of the present invention acrylic acid polymer, Mw is usually in the scope of 2000-20000, preferably in the 3000-15000 scope, more preferably in the 4000-10000 scope.When weight-average molecular weight in this scope, aforementioned (methyl) acrylic acid polymer can be significantly and is shown various performances effectively, as dispersiveness, sequestering power and antigelation performance.Therefore, it can more advantageously be used for such as dispersion agent, during washing agent and detergent builder etc. are used.If the weight-average molecular weight of (methyl) acrylic acid polymer is lower than 2000, this low value may make dispersive ability and sequestering power can not show and limit with being entirely satisfactory the use of this polymkeric substance.On the contrary, if the weight-average molecular weight of (methyl) acrylic acid polymer surpasses 20000, this high value will make polymkeric substance become high polymer and make polymkeric substance can not easily show gratifying water-soluble and resistant to gelling.When using when containing (methyl) acrylic acid polymer (solid) that the aqueous solution of (methyl) acrylic acid polymer obtains and measure number-average molecular weight with purifying polymerization gained by appropriate means, with when containing the determination of aqueous solution number-average molecular weight of (methyl) acrylic acid polymer, as broad as long basically between two kinds of tests with the polymerization gained.Therefore, during test Q value, two kinds of methods all can be used for measuring weight-average molecular weight.
Specifically describe among the embodiment that the weight-average molecular weight (Mw) of mensuration (methyl) acrylic acid polymer and the method for number-average molecular weight (Mn) will be quoted from hereinafter.
Then, when (1) Mw less than 9000 the time, depend on the size of Mw, the dispersity (Mw/Mn) of (methyl) of the present invention acrylic acid polymer is in the scope of 1.5-2.9, preferably in the scope of 1.8-2.7, more preferably in the scope of 2.0-2.5.If dispersity is lower than 1.5, this low value makes the synthetic of polymkeric substance become complicated.On the contrary, if dispersity is higher than 2.9, this high value will can make the amount of stay-in-grade component make downgrade owing to having reduced, and may make (methyl) acrylic acid polymer can not obtain dispersive ability fully satisfactorily, and the possible purposes of polymkeric substance is restricted.Then, when (2) Mw was in the 9000-20000 scope, dispersity was in the scope of 1.5-4.5, preferably in the scope of 2.0-4.0, more preferably in the scope of 2.5-3.5.At this moment, if dispersity is lower than 1.5, this low value makes the synthetic of polymkeric substance become complicated.On the contrary, if dispersity is higher than 4.0, this high value will the amount of the component of controlling quality makes downgrade owing to having reduced effectively.
Calcium-the binding ability of (methyl) of the present invention acrylic acid polymer (sequestering power a kind of) can determine according to Mw.When Mw in the 3000-10000 scope, for example, calcium-binding ability is not less than 235, preferably is not less than 240.If calcium-binding ability is less than 235, this low value makes the washing composition of having introduced this polymkeric substance can't show its washability with being entirely satisfactory.Satisfied the S value requirement of the amount of representing the element sulphur of introducing especially, and preferably further satisfy following required condition, as the R value, iron concentration, with the Q value, and (methyl) of the present invention acrylic acid polymer that its amount of impurities reduces is at (methyl) acrylic acid polymer that is far superior to aspect calcium-binding ability (sequestering power) be proposed before the inventor.Therefore, it can show obviously superb sweat spot and the dirt that is bonded on the fabric are steeped, i.e. decomposition of the spot of calcic component and calcareous tap water and washing are renderd a service.
The tone of (methyl) of the present invention acrylic acid polymer colourless property and transparent aspect be better than existing PSA, the latter presents Huang-brown.When ordinary consumer (client) selected this class to be generally the washing composition of white, they usually even will consider the tone of this class washing composition.Because water white washing composition is better than those and presents yellow person on commercial value, it is highly favourable that colourless and transparent polymkeric substance is proved to be.
The degree of neutralization scope of (methyl) of the present invention acrylic acid polymer does not need special qualification, but can suitably be adjusted to suitable application target.It is usually in the 1-100% scope, preferably in the 20-99% scope, more preferably in the 50-95% scope.
(methyl) of the present invention acrylic acid polymer preferably (methyl) vinylformic acid by containing 50-100mol% and 0-50mol% water miscible can with the formed polymkeric substance of composition polymerization in the aqueous solution of monoene key (monoethylenically) unsaturated monomer of (methyl) acrylic acid copolymer, and be endowed the S value that required condition is represented the amount of the element sulphur of being introduced as described above, and preferred R value, iron concentration and Q value.More preferably this polymkeric substance should be to have with the sulfonic group form to be connected to sulfur-containing group on its end group or the main chain, and the Q value of antigelation performance is lower than (methyl) acrylic acid polymer of 3.0.(methyl) acrylic acid polymer that has satisfied above-mentioned required condition like this has the sulfur-containing group that is connected to polymer terminal group or side chain with the sulfonic group form.Therefore, have higher molecular weight although this polymkeric substance is compared with traditional (methyl) acrylic acid polymer with antigelation performance, its antigelation performance is better than traditional polymkeric substance.And because this polymeric impurities content is low, it can form and obtain best quality and do not sacrifice as dispersiveness the low-molecular weight water-soluble polymer of fundamental propertys such as sequestering power and antigelation performance.Therefore, this polymkeric substance can advantageously be applied to dispersion agent, washing agent, and detergent builder.These (methyl) acrylic acid polymers can by contain 50-100mol% (methyl) vinylformic acid and 0-50mol% water miscible can with the formed polymkeric substance of composition polymerization in the aqueous solution of monoene key (monoethylenically) unsaturated monomer of (methyl) acrylic acid copolymer, it also contains with the sulfonic group form and is connected to sulfur-containing group on its end group or the main chain, and the Q value that has deviated from above-mentioned representative antigelation performance is lower than 3.0 prerequisite.As long as satisfied the S value of the amount of element sulphur that above-mentioned representative is introduced, and preferred R value, the polymkeric substance of prerequisites such as iron concentration and Q value just can show operation of the present invention and effect.(methyl) of the present invention acrylic acid polymer comprise with following monomer as, toxilic acid, fumaric acid, methylene-succinic acid, the acrylic acid multipolymer of 2-hydroxyethyl (methyl), and the multipolymer of quoting in described hereinafter " monomer (II) ", prerequisite is its S value that satisfies the amount of element sulphur that above-mentioned representative is introduced, and preferred R value, prerequisites such as iron concentration and Q value.
The existing low-molecular weight water-soluble polymer that is used for dispersion agent and washing agent, its weight-average molecular weight surpasses at 1000 o'clock, and their antigelation performance promotes with its molecular weight reduction, and require its weight-average molecular weight substantially near 1000 this moment.Simultaneously, its sequestering power promotes with the weight-average molecular weight rising of this water-soluble polymers.Therefore, the traditional water soluble polymer makes three performances, that is, dispersiveness, sequestering power and antigelation performance, meet difficulty in lifting aspect simultaneously.
In contrast, its be contain (methyl) vinylformic acid of 50-100mol% and 0-50mol% water miscible can with the formed polymkeric substance of above-mentioned monomer polymerization in the aqueous solution of monoene key (monoethylenically) unsaturated monomer of (methyl) acrylic acid copolymer, and it is made it to have (methyl) acrylic acid polymer that is connected to the sulfur-containing group on its end group or the main chain with the sulfonic group form immediately, make the Q value of its antigelation performance be lower than 3.0, and satisfy the S value requirement of the amount of representing the element sulphur of introducing (it is for being connected to the sulfur-containing group on polymer terminal group or the main chain with the sulfonic group form).This polymkeric substance preferably satisfies as prerequisites such as R value and iron concentrations.(methyl) like this has excellent dispersive ability and antigelation performance although its weight-average molecular weight of acrylic acid polymer is higher relatively.Especially, because its high weight-average molecular weight attains full and complete satisfaction the antigelation performance.Therefore, satisfy (methyl) acrylic acid polymer of above-mentioned prerequisite, except can be when the tradition with identical approximately weight-average molecular weight (methyl) acrylic acid polymer peer-level shows its sequestering power (ginseng is shown in Table 11 calcium-binding capacity), also show the dispersive ability of height, and good especially antigelation performance (ginseng is shown in Table 11 the Q value of representing the antigelation performance).
As mentioned above, (methyl) of the present invention acrylic acid polymer preferably contains with the sulfonic group form and is connected to sulfur-containing group on its end group or the main chain, has high antigelation performance simultaneously.Because above-mentioned sulfur-containing group as the sulfonic acid end group, this polymkeric substance can improve its dispersive ability and sequestering power.And it can show higher antigelation performance.Therefore, this (methyl) acrylic acid polymer can advantageously be applied to mineral dye dispersion agent, washing agent, and detergent builder.
By aforementioned (methyl) vinylformic acid that contains 50-100mol% and 0-50mol% water miscible can with the formed polymkeric substance of monomer polymerization in the aqueous solution of monoene key (monoethylenically) unsaturated monomer of (methyl) acrylic acid copolymer, has the sulfur-containing group that is connected to its end group or side chain with the sulfonic group form, and the Q value that the antigelation performance is provided is (for the requirement of Q value as previously mentioned) less than 3.0, and the prerequisite of this polymkeric substance will together be narrated with the production method of (methyl) acrylic acid polymer hereinafter.
Second aspect of the present invention is the production method at a kind of (methyl) acrylic acid polymer, it is characterized in that using a kind of initiator, it is one or more combination of persulphate and bisulfite, wherein the bisulfite usage ratio is as 1 o'clock with the persulphate quality, its mass ratio is 0.5-5, the total amount that adds the persulphate of polymerization reaction system and bisulfite should be in every mole of 2-20g treats the monomeric scope of polymeric, and polymerization temperature is in the 25-99 ℃ of scope.
According to aforementioned proportion persulphate and bisulfite are added as initiator simultaneously, can prevent that (methyl) acrylic acid polymer product unnecessarily is converted into superpolymer and produces low-molecular weight polymer with remaining valid.Except this advantage, product (methyl) acrylic acid polymer can be introduced the sulfur-containing group of sulfonic group form therein quantitatively, that is, its amount makes the S value of amount of the element sulphur that above-mentioned representative is introduced drop in the scope mentioned above.The sulfur-containing group of this sulfonic group form can be introduced quantitatively shows that persulphate and bisulfite can be used as initiator satisfactorily.Therefore, this polymerization reaction system does not need to add excessive initiator and makes the amount of the initiator that added further reduce.The result is that it makes the raising of polymeric articles cost be inhibited, and enhances productivity.Therefore, (methyl) acrylic acid polymer of being produced, can suppress with for example, the gathering of calcium metal-salt, and obtain gratifying antigelation performance.In addition, the amount of the initiator by will adding polymerization reaction system and polymeric reaction temperature control can suppress a large amount of generations of sulfurous gas and the generation of corresponding minimizing impurity within the specific limits.Therefore, can realize the further raising of quality product, the rising of polymer production cost is inhibited, and production efficiency can improve.
Monomer in the production method of the present invention need not limit especially, only needs it to contain the monomer component that can obtain (methyl) acrylic acid polymer by polymerization.It need contain (methyl) vinylformic acid (below be sometimes referred to as monomer (I)) at least.Choose wantonly, its can contain can with water-soluble mono ethylene linkage (monoethylenically) unsaturated monomer of (methyl) acrylic acid copolymer (below be sometimes referred to as monomer (II)) and/or other monomers (below be sometimes referred to as monomer (III)).Term used herein " monomer " refers to the part that is formed by the monomer component and does not comprise other components such as the solvent that is used for polymerization process, initiator and other additives.
As the example of monomer (I), what can quote from is vinylformic acid and methacrylic acid.These monomers can use separately or in combination.Preferably, be vinylformic acid self or vinylformic acid and methacrylic acid mixture with the formation of aforementioned mixed.
Usually in the scope of 50-100mol%, preferably in the scope of 70-100mol%, more preferably in the scope of 90-100mol%, it is the ratio based on the monomer total amount to the amount of monomer (I) in aforementioned monomer.If the quantity not sufficient 50mol% of monomer (I) wherein, the disadvantage of this low value is to make sequestering power and antigelation power balance to show harmoniously.Simultaneously, be limited to 100mol% on this amount, promptly monomer can all be made up of (methyl) vinylformic acid.In addition, when vinylformic acid and methacrylic acid combination compositing monomer (I), wherein the amount of methacrylic acid should be avoided surpassing 5mol%, and preferably it drops in the scope of 0.5-4mol%, more preferably in the scope of 1-3mol%.If wherein the amount of the methacrylic acid of Yin Ruing surpasses 5mol%, this high value may cause the decline of sequestering power.
Monomer (I) can add in the solvent, and it will be in hereinafter specifically describing, and preferably with the form of the solution (be preferably the aqueous solution) of monomer (I) in water.When monomer (I) used with solution (being preferably the aqueous solution) form, its concentration range was generally 10-100 weight %, preferably in 30-95 weight % scope, more preferably in 50-90 weight % scope.If the concentration less than 10 weight % of monomer in the solution (I), this low value will make product concentration reduce and make the conveying of product and store complicated.The upper limit of this concentration does not need special qualification.This concentration can be 100 weight % (promptly wholes') monomer (I) (solution), that is, this solution does not contain solvent fully.
As can with the example of water-soluble mono ethylene linkage (monoethylenically) unsaturated monomer of (methyl) acrylic acid copolymer, can quote from, but not exclusive having, aforementioned monomer (II), (methyl) vinylformic acid, i.e. monomer (I) part neutralization or fully in and the salt of gained basic metal such as sodium or potassium; Monomer (I) and ammonia or as the organic amine of monoethanolamine or trolamine, partially or completely in gained salt; Monoene key unsaturated aliphatic monocarboxylic acid such as Ba Dousuan and hydroxyl acrylic; Aforementioned monoene key unsaturated aliphatic monocarboxylic acid partly neutralize or fully in and the gained an alkali metal salt; Aforementioned monoene key unsaturated aliphatic monocarboxylic acid and ammonia or as the organic amine of monoethanolamine or trolamine partially or completely in and gained salt; As toxilic acid, the monoene key unsaturated aliphatic dicarboxylic acid of fumaric acid and methylene-succinic acid; Aforementioned monoene key unsaturated aliphatic dicarboxylic acid partially or completely in and gained salt; Aforementioned monoene key unsaturated aliphatic dicarboxylic acid and ammonia or as the organic amine of monoethanolamine or trolamine partially or completely in and gained salt; As vinyl sulfonic acid, allyl sulphonic acid and 3-alkoxyl group-3-hydroxypropyl sulfonic acid contain sulfonic monoethylenically unsaturated monomer; Aforementioned monoethylenically unsaturated monomer partially or completely in and the gained an alkali metal salt; Aforementioned monoethylenically unsaturated monomer and ammonia or as the organic amine of monoethanolamine or trolamine partially or completely in and gained salt; Reach the unsaturated hydrocarbons that contains hydroxyl as 3-methyl-2-butene-1-alcohol (abbreviating prenol sometimes as) and 3-methyl-3-butene-1-alcohol (abbreviating isoprenol sometimes as).
Monomer (II) can suitably be selected from the above all cpds of enumerating, can be separately or two or more uses that combine.In above-listed compound, the preferred use is selected from the unsaturated aliphatic dicarboxylic acid, contains the sulfonic group unsaturated hydrocarbons, with these compounds partially or completely in and gained salt in one or more compounds, because it has excellent especially sequestering power, dispersiveness and antigelation ability.
Usually in the scope of 0-50mol%, preferably in the scope of 0-30mol%, more preferably in the scope of 0-10mol%, it is the ratio based on the monomer total amount to the usage quantity of monomer (II) in monomer.If the amount of the monomer of introducing (II) surpass 50mol%, this high value may cause sequestering power to descend.Simultaneously, because monomer (II) is the component of choosing wantonly, the following 0mol% that is limited to of its content.Use the homopolymer of aforementioned monomer (I) component or multipolymer even under the situation of not using monomer (II), also can show effect of the present invention and effect fully satisfactorily.
Monomer (II) dissolves in the solvent, and it will be in hereinafter specifically describing, and preferably in water, and uses with the form of the solution (being preferably the aqueous solution) of monomer (II).When monomer (II) used with monomer (II) solution (being preferably the aqueous solution) form, its concentration range was generally 10-100 weight %, preferably in 20-95 weight % scope, more preferably in 30-90 weight % scope.If the concentration less than 10 weight % of monomer in the solution (II), this low value will make product concentration reduce and make the conveying of product and store complicated.Simultaneously, the upper limit of this concentration does not need special qualification.This concentration can be 100 weight % (promptly wholes') monomer (II) (solution), that is, this solution does not contain solvent fully.
Be different from above-mentioned monomer (I) and monomer (II) (III) need not limit especially.As the example of spendable monomer (III) herein, citable have a hydrophobic monomer, promptly as (methyl) acrylate, vinyl pyrrolidone, vinyl ether, vinylbenzene, (methyl) methyl acrylate and (methyl) vinylformic acid ethyl ester of vinyl-acetic ester.Such monomer (III) can suitably be selected from above-listed compound, and it can be one of them and uses separately or use with two or more combining form wherein.When hydrophobic monomer is used as monomer (III), although it is disperseing excellent performance aspect the hydrophobic nature compound, it may influence the antigelation performance of (methyl) acrylic acid polymer that produces.Therefore, the amount of the monomer of introducing (III) must limit according to its selecteed purposes.
When above-mentioned hydrophobic monomer is used as monomer (III) introducing, usually the amount of monomer (III) component of being introduced should be avoided surpassing 40mol% and preferably dropping in the scope of 0-20mol%, and more preferably in the scope of 0-10mol%, this value is for based on the monomer total amount.In other words, the amount of the hydrophilic monomer of being introduced that combines above-mentioned monomer (I) and monomer (II) (promptly comprise and be no less than the acrylic acid hydrophilic monomer of 50mol% (methyl)) surpasses 60mol% usually and preferably drops in the scope of 80-100mol%, and more preferably in the scope of 90-100mol%, this value is for based on the monomer total amount.If the amount of the hydrophobic monomer of the above-mentioned monomer of introducing (III) surpasses 40mol% (being the above-mentioned quantity not sufficient 60mol% that combines the hydrophilic monomer of monomer (I) and monomer (II) that is introduced), the low-molecular weight polymer that is produced obtains as patent US3, the solubleness of being explained in 546,099 in water.The Q value of the representative antigelation performance that (methyl) acrylic acid polymer that is produced in addition, may obtain to increase also may not obtain outstanding antigelation performance.
Monomer (III) dissolves in the solvent (being preferably organic solvent), and it will be in hereinafter specifically describing, and adds with the form of the solution of monomer (III).So the concentration range of the solution of the monomer (III) that uses is generally 10-100 weight %, preferably in 20-95 weight % scope, more preferably in 30-90 weight % scope.If the concentration of monomer in the solution (III) is lower than 10 weight %, this low value will make product concentration reduce and make the conveying of product and store complicated.Simultaneously, the upper limit of this concentration does not need special qualification.This concentration can be 100 weight % (promptly wholes') monomer (II) (solution), that is, this solution can not contain solvent fully.
The inventive method preferably makes above-mentioned monomer carry out polymerization in the aqueous solution.This aqueous solution contains solvent, initiator and other additives.
Be used for monomer herein, and be preferably like water solvent such as water alcohol, ethylene glycol, glycerine, or polyoxyethylene glycol at the solvent that the aqueous solution carries out the polymeric polymerization reaction system.Water is particularly preferred.These can use separately like water solvent or use with two or more member's bonded forms.For the solubleness of above-mentioned monomer in this solvent is improved, can in water solvent, suitably add organic solvent, its ratio should not produce negative interaction to monomer polymerization.
Specifically, as organic solvent, can suitably select lower alcohol such as methyl alcohol and ethanol for use; Acid amides such as dimethylformaldehyde; With one or more members in ether such as dme and the dioxane.
The common scope of above-mentioned solvent load is 40-200 weight %, and preferably in 45-180 weight % scope, more preferably in 50-150 weight % scope, this value is based on the monomer total amount.If this solvent load less than 10 weight %, this low value will make molecular weight improve.On the contrary, when its amount surpasses 200 weight %, this high value will make the concentration of (methyl) acrylic acid polymer of generation reduce and may need to remove solvent for use.Most of or whole solvents should drop in the reaction vessel in the starting stage of polyreaction.Partial solvent can add (dropwise) reactive system separately in polymerization process.In addition, solvent should with the monomer component, initiator component and other additives together, the form that is dissolved in advance in this solvent with these components suitably adds (dropwise) reactive system.
Above-mentioned polymkeric substance carries out being used in the polymeric process polymerization reaction system in the aqueous solution initiator is preferably one or more combination of persulphate and bisulfite.By using this initiator, can on end group or side chain, introduce sulfonic group quantitatively, obtain the low-molecular weight water-soluble polymer product, its antigelation performance and dispersed and sequestering power excellence, and can show effect of the present invention and effect effectively.When in initiator system, introducing persulphate, also introduce bisulfite, can prevent that the polymkeric substance that produces is converted into unnecessary polymer and can produces low-molecular-weight polymkeric substance effectively.
As the example of above-mentioned persulphate, citable have Sodium Persulfate, a Potassium Persulphate, and ammonium persulphate.As the example of bisulfite, citable have Sodium Metabisulphate 65, a potassium acid sulfite, and ammonium bisulfite 56to 70.Alternative this bisulfite of sulphite or pyrosulfite.
Add persulphate and bisulfite ratio be, based on the persulphate of a weight part, the scope of the amount of bisulfite is the 0.5-5 weight part, preferable range is the 1-4 weight part, more preferably scope is the 2-3 weight part.If the amount based on the bisulfite of the persulphate of a weight part is lower than 0.5 weight part, this low value fully shows the effect of bisulfite unsatisfactorily, and as a result of, may introduce sulfonic group to the end group of polymkeric substance to satisfy the aforementioned amount of the S value of the element sulphur amount of being introduced of representing, but also the weight-average molecular weight of (methyl) acrylic acid polymer is increased.On the contrary, if the amount based on the bisulfite of the persulphate of a weight part surpasses 5 weight parts, this high value will make the introducing amount too much (unnecessary waste) of the bisulfite that adds in the polymerization reaction system and the effect of bisulfite can not be showed with share is proportional with adding, excessive bisulfite is decomposed in polymerization reaction system and generate a large amount of sulfurous gas, a large amount of impurity that produce in (methyl) acrylic acid polymer, and the final quality that reduces (methyl) acrylic acid polymer that generates and at product lay up period generation contamination precipitation at low temperatures.
As the persulphate of initiator adding and the amount of bisulfite be, total weight range of the persulphate of initiator and bisulfite is every mole of monomer 2-20 gram, and preferable range is the 4-15 gram, and more preferably scope is the 6-12 gram, and also preferred scope is the 6-9 gram.Although persulphate and bisulfite add with so little amount, the present invention is reduced to lower level as a contributive factor by the temperature with polyreaction, can significantly reduce the generation of impurity in the generation of sulfurous gas and the production process.As a result, sulfonic group can be introduced on the end group or side chain of (methyl) acrylic acid polymer that is generated as sulfur-containing group, and its amount satisfies the requirement that the S value of element sulphur amount is introduced in the above representative that defines.Its also can prevent the decline of quality of (methyl) acrylic acid polymer of being generated and product at low temperatures lay up period produce contamination precipitation.If the persulphate of the initiator that adds and the total amount of bisulfite are lower than 2 grams, this low value will finally improve the molecular weight of the polymkeric substance that generates, may make as the sulfonic group of sulfur-containing group can not be introduced into the amount of requirement that the S value of element sulphur amount is introduced in the representative of satisfying above definition generated on the end group of (methyl) acrylic acid polymer, tend to increase the weight-average molecular weight of this polymkeric substance.On the contrary, if total amount surpasses 20 grams, the disadvantage of this high value be to make the persulphate of initiator and bisulfite result of use can't share is proportional to be showed with adding, and produce the such negative interaction of purity decline that makes (methyl) acrylic acid polymer that generates.
Above-mentioned persulphate as one of initiator species dissolves in above-mentioned solvent, in the preferably water, and adds with the form of persulfate solution (preferred aqueous solutions).The concentration range of the persulphate that uses with the form of persulfate solution (preferred aqueous solutions) is 1-35 weight %, and preferable range is 5-35 weight %, and more preferably scope is 10-30 weight %.If the concentration of persulphate is lower than 1 weight %, this low value makes concentration reduce the most at last and makes the conveying of product and store complicated.On the contrary, if the concentration of persulphate surpasses 35 weight %, this high value may produce the precipitation of persulphate.
Bisulfite as one of initiator species dissolves in above-mentioned solvent, in the preferably water, and adds with the form of bisulfite solution (preferred aqueous solutions).The concentration range of the bisulfite that uses with the form of bisulfite solution (preferred aqueous solutions) is 10-40 weight %, and preferable range is 20-40 weight %, and more preferably scope is 30-40 weight %.If the concentration of bisulfite is lower than 10 weight %, this low value makes product concentration reduce the most at last and makes the conveying of product and store complicated.On the contrary, if the concentration of bisulfite surpasses 40 weight %, this high value may produce the precipitation of bisulfite.
The present invention does not get rid of the embodiment pattern of other initiators of other use (comprising chain-transfer agent).The initiator of like this other can suitably use when needs use, and its amount produces any detrimentally affect for being not enough to effect of the present invention.In the present invention, the combination of above-mentioned persulphate and bisulfite can be advantageously used in initiator system.This initiator does not need to be restricted to especially this combination.The present invention can introduce sulfonic group as sulfur-containing group, and its amount satisfies the requirement of the S value of above definition.Also can use the initiator system that can in one-step polymerization, produce low-molecular weight polymer herein.
As other initiators example of (comprising chain-transfer agent), can quote from has azo compound as 2,2 '-azo two (2-amidine propane) hydrochloride in this, 4,4 '-azo, two-4-cyanovaleric acid, azo Di-Isobutyl nitrile, with 2,2 '-azo two (4-methoxyl group-2,4-methyl pentane nitrile; Organo-peroxide such as benzoyl peroxide, lauroyl peroxide, peracetic acid, ditertiary butyl peroxide and cumene hydroperoxide hydrogen; And hydrogen peroxide.
Such initiator also dissolves in above-mentioned solvent, in the preferably water, and uses with the form of solution (preferred aqueous solutions).The initiator concentration scope of using with the form of solution (preferred aqueous solutions) only needs it to avoid effect of the present invention is had a negative impact.Usually, can suitably it be decided to be identical with the concentration of aforementioned persulphate or bisulfite.
For the additive that can use in the polymerization reaction system during polymerization in the aqueous solution in aforementioned monomer beyond the initiator, the add-on of suitable additive should be avoided operation of the present invention and effect are produced negative interaction.For example, for the heavy metal concentration conditioning agent, organo-peroxide, hydrogen peroxide and metal-salt can be used as this class additive.
Aforementioned heavy metal concentration conditioning agent need not limit especially.Can use polyvalent metal compounds or simple material.As the example of heavy metal concentration conditioning agent, that can quote from has, water-soluble polyvalent metal salt such as vanadylic chloride, vanadium trichloride, vanadyl oxalate, vanadyl vitriol, vanadic anhydride, ammonium meta-vanadate, inferior the vanadium [(NH of ammonium sulfate thiosulfuric acid 4) 2SO 4VSO 46H 2O], inferior vanadium ammonium sulfate [(NH 4) V (SO 4) 212H 2O], acetate mantoquita (II), copper (II), cupric bromide (II), etheric acid copper (II), chlorination divalence cuprammonium, cupric ammonium chloride, copper carbonate, cupric chloride (II), citric acid copper (II), Tubercuprose (II), copper hydroxide (II), cupric nitrate (II), copper naphthenate, cupric oleate (II), toxilic acid copper, cupric phosphate, copper sulfate (II), cuprous chloride, cupric cyanide (I), cupric iodide, cupric oxide (I), cupric thiocyanide, ethanoyl ironic acetate, ferric ammonium citrate, Ferrox ammonium, ferric ammonium sulfate, ferrous ammonium sulphate, ironic citrate, ferrous fumarate, toxilic acid iron, iron lactate, iron nitrate, pentacarbonyl iron, tertiary iron phosphate, and ferric pyrophosphate; Polyvalent metal oxides, as, vanadium pentoxide, cupric oxide (I), iron protoxide, and ferric oxide; Polyvalent metal sulfide, as iron sulphide (III), iron sulphide (II), and cupric sulfide; And copper powder and iron powder.
For the present invention, the scope of the heavy metal concentration of (methyl) acrylic acid polymer that generates is preferably 0.05-10ppm.Therefore, recommendable is suitably to add aforementioned heavy metal concentration conditioning agent with appropriate amount.The inventor also finds when making reaction vessel, the reaction vessel inwall that its steel or copper base alloy are made has added that glass-lined is to optimize its corrosion resistance, and container and agitator are made with stainless steel (SUS), heavy metal ion then, iron ion particularly, to under working condition of the present invention,, go into reaction soln with suitable as defined above amount liquate (providing) on container and other materials from SUS.Provide ion to say it is favourable with upper type from the cost performance angle.Method produced according to the invention, the agitator that uses such conversion unit to make as reaction vessel and SUS can show and add above-mentioned heavy ion concentration regulator identical operations and effect.Although there is not any problem in the reaction vessel that existing steel or copper base alloy are made, it may be with excessive concentration liquate metal ion.Use existing reaction vessel to be proved to be uneconomic, come from adding lustre to of heavy metal ion, and and then need increase to remove the operation of heavy metal ion because the liquate of heavy metal ion produces inevitably.The reaction vessel that carries out the glass-lined processing can not produce any problem and allow to use where necessary the heavy metal concentration conditioning agent with particular requirement.
The common scope of the polymerization temperature of the polyreaction of aforementioned monomer is 25-99 ℃.This polymerization temperature preferably is not less than 50 ℃, more preferably is not less than 70 ℃.Polymeric reaction temperature preferably is not higher than 95 ℃ more preferably no higher than 90 ℃.Polymerization even can carry out being lower than under 90 ℃ the temperature.If polymerization temperature is lower than 25 ℃, this low value can make molecular weight increase and impurity is increased, and makes the excessive prolongation of polymerization time that production efficiency is descended.On the contrary, if polymerization temperature is higher than 99 ℃, this high value will make the bisulfite of initiator decompose and a large amount of sulfurous gas that discharges, then make and produce impurity after dissolving in sulfurous gas and polymerization in the liquid phase, need from system, to discharge sulfurous gas in addition and need in polymerization process, carry out expensive recovery and the processing of discharging sulfurous gas, and, because bisulfite is overflowed with the sulfurous gas form in the initiator, making institute add initiator can not can not resemble needed low to show its effect and molecular weight pro rata with add-on with being entirely satisfactory.Explanation in passing, term as used herein " polymerization temperature " refers to the temperature of reaction soln in the reactive system.
Polymerization temperature does not need roughly to keep consistently on a fixed level.Can, for example, initiated polymerization under common room temperature (it is usually less than 25 ℃, because the transient deviation of polymerization temperature and aforementioned range does not depart from scope of the present invention), be warming up to the temperature of regulation with the suitable heating-up time (or temperature rise rate), and keep the temperature of regulation then.In addition, the time length that dropwise adds of components such as monomer that dropwise adds and initiator can have nothing in common with each other.With regard to dropwise adding mode, temperature may change (raising or reduction) in the aforementioned temperature scope in the time course of polymerization process.Dropwise add mode and need not limit especially, only need it not weaken operation of the present invention and effect..
Especially, in polyreaction in the method (being the room temperature initiating method) that normal room temperature causes, when institute's qualification process was 300 minutes, for example, polyreaction can following method be carried out, in during promptly 120 minutes, preferably in 0-90 minute scope, more preferably reached in the scope at 0-60 minute design temperature (only need it above defining in the polymerization temperature scope, preferred 70-90 ℃, more preferably about 80-90 ℃), and stop down to polyreaction remaining on such design temperature thereafter.If temperature-rise period is different from above-mentioned scope, deviation may cause (methyl) acrylic acid polymer that generates to be grown to unnecessary superpolymer.Polymerization process is set to describe as illustration in 300 minutes.If polymerization is set to different processes, recommend its temperature-rise period be set to previous example in the intensification process of polyreaction be the intensification process of similar proportion.
The pressure of reactive system need not limit especially during the polyreaction of aforementioned monomer.Polyreaction can be at normal pressure (normal atmosphere), decompression, or carry out under the high pressure, as long as it is fit to requirement best.Discharge sulfurous gas for stoping in the polymerization process, and can obtain the reduction of molecular weight, recommend to make to be aggregated under normal pressure or the high pressure in the reactive system of sealing and carry out.Carry out under normal pressure (normal atmosphere) when polyreaction, reactive system neither needs to increase supercharging equipment or pressure regulating equipment, does not also need to use the reaction vessel and the pipe connecting piece that can keep-up pressure.Therefore, normal pressure (normal atmosphere) is said so preferably from the production cost angle.That is, the setting of optimum pressure condition can be depending on the purposes of (methyl) acrylic acid polymer of producing.
For the atmosphere in the reactive system,, preferably use rare gas element although can use the undressed form of air.For example, recommend reactive system inside is replaced by the rare gas element as nitrogen before polyreaction begins.Then, the gas (such as, for example, oxygen) that constitutes reactive system atmosphere is dissolved in the liquid phase and finishes the function of stopper then.The result is, it can stop as the persulphate inactivation of initiator and reduction and molecular weight is further reduced.
In production method of the present invention, the polyreaction of aforementioned monomer is preferably carried out under acidic conditions.By using the tart polymeric reaction condition, can suppress the increase of viscosity in aqueous solution in the polymerization reaction system and can produce low-molecular-weight (methyl) acrylic acid polymer satisfactorily.Because polyreaction is carried out under more aforementioned higher concentration, it can further significantly improve production efficiency.Especially, by in polymerization process, degree of neutralization being reduced to the scope of 1-25mol%, can strengthen reducing the effect of aforementioned amount of initiator synergistically and significantly optimize the effect that reduces impurity.In addition, preferably in polymerization process, in 25 ℃ of pH regulator with reaction soln to the scope of 1-6.By under such acidic conditions, carrying out polyreaction, can in a step, finish polymerization simultaneously in high density.Therefore, it can save the enrichment step that may need in the conventional production method.Therefore, the production efficiency of (methyl) acrylic acid polymer can significantly improve and the rising of production cost can be suppressed.
In aforementioned acidic conditions, the pH of the reaction soln in the polymerization process under 25 ℃ is in the 1-6 scope, preferably in the 1-5 scope, more preferably in the 1-4 scope.If pH is less than 1, this low value may cause producing the discharging of sulfurous gas and equipment is corroded.On the contrary, if pH surpasses 6, this high value will cause the reduction of bisulfite efficient and exceedingly improve molecular weight.
Example as the pH regulator agent that is used in polymerization process, reaction soln being adjusted to aforementioned pH, can quote from having in this, alkali metal hydroxide such as sodium hydroxide and potassium hydroxide, alkaline earth metal hydroxides such as calcium hydroxide and magnesium hydroxide and organic amino salt such as ammonia, monoethanolamine, and trolamine.These pH regulator agent can be used separately or use with two or more bonded forms.Other above-listed pH regulator agent relatively, alkali metal hydroxide such as sodium hydroxide and potassium hydroxide are preferred, and sodium hydroxide is particularly preferred.In this manual, this pH regulator agent can be called " a kind of pH regulator agent " or " a kind of neutralizing agent " sometimes simply.
The degree of neutralization of polymerization process is in the 1-25mol% scope.When above-mentioned monomer (I) was configured for the polymeric monomer alone, degree of neutralization was preferably in the 2-15mol% scope, more preferably in the 3-10mol% scope.When the used monomer of polymerization also comprises monomer (II) except that above-mentioned monomer (I), part or all of monomer (II) can be added reactive system in the polymerization starting stage.At this moment, the degree of neutralization of polymerization process is preferably in the 1-25mol% scope, more preferably in the 3-10mol% scope.As long as the degree of neutralization of polymerization process falls within this scope, when aforementioned monomer (I) uses alone or during when monomer (I) and monomer (II) copolymerization, polymerization or copolymerization all can realize most effectively.It also can obtain low-molecular-weight polymkeric substance under the condition that does not increase viscosity in aqueous solution in the polymerization reaction system.And, owing to polyreaction can be carried out under than the concentration of preamble gained higher level, so production efficiency can significantly improve.If the degree of neutralization of polymerization process is lower than 1mol%, this low value may cause the amount of the sulfurous gas that discharges to increase and improve molecular weight.On the contrary, if the degree of neutralization of polymerization process surpasses 25mol%, this high value will make the chain transfer efficiency of bisulfite reduce and increase molecular weight.This high value also can increase viscosity in aqueous solution in the polymerization reaction system significantly in the process that polymerization is carried out, the molecular weight of the polymkeric substance that generates is unnecessarily improved and low-molecular-weight polymkeric substance can't be produced, the effect that reduces degree of neutralization can not be showed fully satisfactorily, and make a large amount of minimizing impurity become difficult.
Herein, the neutral method is not done special qualification.As neutralizing agent, can use alkaline monomer (II) component as (methyl) sodium acrylate.Also allow in addition to use alkali metal hydroxide such as sodium hydroxide to replace.Choose wantonly, it can be used in combination.The neutralizing agent that adds in the N-process can be solid form or for appropriate solvent, preferably water, aqueous solution form.When using the aqueous solution, the concentration range of the aqueous solution is 10-60 weight %, preferred 20-55 weight %, more preferably 30-50 weight %.If concentration of aqueous solution is lower than 20 weight %, this low value will make production concentration reduce and make the conveying of product and storage become complicated.On the contrary, if concentration surpasses 60 weight %, this high value may produce precipitation, increase viscosity, and it is complicated that solution is carried.
For polymerization is prepared, monomer, the persulphate of initiator system and bisulfite, usually be dissolved in advance in the appropriate solvent (solvent phase that is preferably used solution when dropwise reinforced with solvent) to make monomer solution with other additives, persulfate solution, bisulfite solution, and other additive solutions.Polymerization preferably dropwise is added to constantly in the section at the appointed time at solution and continues to carry out when inserting (moisture) solvent (randomly being adjusted to specified temperature) in the molten device of reaction in advance.In addition, the partially aqueous solvent can (see Table 1 embodiment that gives 6) with inserting in advance that solvent in the reaction vessel separates and dropwise add in the polymerization reaction system in the polymerization starting stage thereafter.But production method of the present invention is not limited to present described method.For the method that dropwise adds, for example, dropwise add and continuously or to be divided into a plurality of segments and to carry out discontinuously.The all or part of of monomer (II) can add reactive system (be that monomer (II) all or part of can be considered moment and dropwise add, and post polymerization beginning) in starting stage of polyreaction.In addition, for example, the speed that monomer (II) dropwise adds (dropwise add-on) is from the beginning to dropwise add finishing to keep constant (quantitatively), or the speed (dropwise add-on) of dropwise adding process change in time, and this depends on polymerization temperature.Be not that all components that dropwise add are dropwise added with identical speed, each dropwise adds the time that component begins dropwise to add and the time that finishes dropwise to add staggered mutually, or its process that dropwise adds is shortened or prolongs.Therefore, production method of the present invention allows so suitable change to avoid influencing operation of the present invention and effect.When each component dropwise adds fashionablely separately with the solution form, dropwise the solution of Jia Ruing can be heated to the level identical with the polymerization temperature of reactive system in advance.When operation like this, polymerization temperature when it need remain on steady temperature following time, will only produce little change and be easy to and regulate.
As monomer (I), (II), and/or (III) and will be in specifically described monomer A hereinafter, B, and/or during the C copolymerization, the process that each monomer dropwise adds should be controlled, this depends on each monomeric polymerization.For example, when using the monomer of oligomerization ability, dropwise the process of Jia Ruing should shorten.Also allowing will this monomeric all or part of associated vessel that places in advance in the reactive system.
In addition, the effect of bisulfite is that the molecular weight of polyreaction starting stage greatly affects its final molecular weight.Therefore, for reducing initial molecular weight, recommend part, the bisulfite of 5-20 weight % or its solution begin to add (dropwise) reactive system in back 60 minutes in polymerization, preferably in 30 minutes, more preferably in 10 minutes.This method is particularly effective in the occasion that room temperature causes in polymerization.
Between polymerization period, the more important thing is discharging that suppresses sulfurous gas and the generation that stops impurity by the reduction polymerization temperature.For this reason, all processes that dropwise adds in the polymerization process need fall within 180-600 minute scope, in the preferred 210-480 minute scope, more preferably in 240-420 minute scope.But,, prolong polymerization time and also can be used as a most important method in view of the aforementioned problem that is run in process of production reaches the quality that generates polymkeric substance in order to improve.If dropwise all processes of Jia Ruing is less than 180 minutes, this low value will make as the persulfate solution of initiator system adding and the effect of bisulfite solution and can not show effectively easily, thereby make with the sulfonic group form and introduce end group of (methyl) acrylic acid polymer that generated or the requirement that the sulfur-containing group on the side chain is difficult to satisfy the S value of representing the element sulphur amount of being introduced, then make polymkeric substance obtain higher weight-average molecular weight, may produce the excessive of initiator owing to the process that dropwise adds is short in reactive system, and cause the decomposition of excessive initiator, discharge sulfurous gas, make it from system, to overflow, impurity level is increased.But the main points of correct technology are to limit polymerization temperature and amount of initiator are in the low scope, and it can not be thought, and the described problem that relates to conventional art can actually take place.This explanation distinguishes itself and various other polymerizing conditions well.On the contrary, if dropwise the whole process of Jia Ruing was above 600 minutes, although the polymkeric substance that generates have excellent quality owing to the discharging of sulfurous gas is suppressed, this high value will make the production efficiency of (methyl) acrylic acid polymer reduce and may limit the use of the polymkeric substance that produces.Term used herein " the dropwise whole process of Jia Ruing " refers to dropwise add fashionable process till when last component that dropwise adds (being not necessarily limited to a component) dropwise adds end from first component that dropwise adds (being not limited to a component) beginning.
In the component that other dropwise add, the process that bisulfite or its solution dropwise add in polymerization process, its terminal point is led over the interval in the moment of the terminal point that dropwise adds of monomer (I) or its solution constantly should be 1-30 minute scope, preferable range is 1-20 minute, and more preferably scope is 1-15 minute.By this method, can reduce polymerization and finish the amount of back bisulfite and reduce the quantity discharged of sulfurous gas efficiently and effectively and by the formed impurity of bisulfite.Therefore, the amount that sulfurous gas dissolves in the formed impurity of liquid phase in the gas phase after being finished by polymerization can significantly be reduced.When still existing when bisulfite even after polymerization is finished, it can make impurity increase and cause the reduction of polymer quality, and is settled out impurity in product low tempertaure storage process.Therefore, the initiator that contains bisulfite preferably should be consumed to fully when polymerization is finished and exhaust.
Be no less than one minute the timed interval if the termination that monomer (I) dropwise adds can't be taken the lead constantly by the termination that dropwise adds of bisulfite solution constantly, bisulfite just may still exist after polymerization is finished.This class situation comprises the situation that the terminal point that dropwise adds of terminal point that bisulfite or its solution dropwise add and monomer (I) or its solution reaches simultaneously, and the terminal point that dropwise adds of bisulfite (solution) lags behind the situation of the terminal point that monomer (I) (solution) dropwise adds.In these cases, be difficult to suppress efficiently and effectively the discharging of sulfurous gas and the formation of impurity, and residual initiators may there be negative impact to the thermostability of product polymkeric substance.On the contrary, if the termination timed interval constantly that the leading constantly monomer (I) (solution) of the termination that dropwise adds of bisulfite or its solution dropwise adds surpasses 30 minutes, bisulfite has used up when polymerization stops.This bisulfite exhaust the increase that may cause molecular weight fully.In addition, because bisulfite is dropwise to add in large quantities in the short period span in the polymerization process, because the speed that bisulfite dropwise adds is higher than the speed that monomer (I) (solution) dropwise adds, so the impurity that produces in adition process dropwise and the amount of sulfurous gas may increase.
In the component that other dropwise add, the scope that the terminal point that persulphate (solution) dropwise adds in polymerization process lags behind the terminal point that monomer (I) (solution) dropwise adds constantly is 1-30 minute the timed interval, preferable range is 1-20 minute, and more preferably scope is 1-15 minute.By this delay, monomeric residual volume and reduce the impurity that produces by residual monomer significantly after can reducing polymerization and finishing.
If the terminal point that persulphate (solution) dropwise adds lags behind the timed interval of the terminal point that monomer (I) (solution) dropwise adds constantly and is less than one minute, the monomer component produced remaining after this low value may make polymerization finish, this class situation comprises the situation that terminal point that terminal point that persulphate (solution) dropwise adds and monomer (I) (solution) dropwise add reaches simultaneously, and the terminal point that dropwise adds of persulphate (solution) lags behind and the situation of the terminal point that monomer (I) (solution) dropwise adds.In these cases, the formation that suppresses impurity efficiently and is effectively met difficulty.On the contrary, if the terminal point that persulphate (solution) dropwise adds lags behind terminal point timed interval constantly that monomer (I) (solution) dropwise adds constantly more than 30 minutes, persulphate or its degradation production have residue and formation impurity polymerization is finished after.
Each component dropwise adds end, and when the polyreaction in the polymerization reaction system stops, solid constituent concentration in the aqueous solution (i.e. the concentration of the solid constituent that is produced by monomer polymerization) surpasses 35 weight % and usually preferably in 40-70 weight % scope, more preferably in 45-65 weight % scope.As long as solid constituent concentration surpassed 35 weight % when polyreaction finished, polymerization can be carried out in a step under high density.Therefore, can obtain low-molecular-weight (methyl) acrylic acid polymer efficiently.For example, required enrichment step can save in the conventional production methods.Therefore, can enhance productivity significantly.As a result, can improve the production efficiency of (methyl) acrylic acid polymer and suppress the raising of production cost.
If above-mentioned solid constituent concentration is lower than 35 weight %, for example, this low value may can't significantly improve the production efficiency of (methyl) acrylic acid polymer owing to not saving enrichment step.
In the traditional method situation, the solid constituent concentration that improves polymerization reaction system has run into problem, promptly owing to the carrying out of polyreaction significantly improves the viscosity of reaction soln the weight-average molecular weight of the polymeric articles that generates is significantly increased.When polyreaction is carried out (25 ℃ following pH drop in the 1-6 scope and degree of neutralization drops in the 1-25mol% scope) under acidic conditions, because the raising of the reaction soln viscosity that causes of polyreaction can be suppressed.Therefore, even polyreaction is carried out under high density, the production efficiency that still can obtain low-molecular-weight polymkeric substance and polymkeric substance can significantly improve.
Term used herein when stopping " polyreaction " may be interpreted as in this moment all dropwise addings that dropwise add component have been finished and has still preferably referred to the moment that the ageing process of defined (polymerization is finished) has thereafter been finished.
Above-mentioned ageing process is usually in 1-120 minute scope, preferably in 5-60 minute scope, more preferably in 10-30 minute scope.If ageing process is less than 1 minute, thereby this low value may be owing to fail abundant ageing and make the monomer component that residue be arranged and may produce the impurity that comes from residual monomer and make the quality reduction.On the contrary, if ageing process is higher than 120 minutes, this high value will make polymeric solution add lustre to.In addition, the continuation maintenance to completed polymerization and polymerization temperature is uneconomic.
In the ageing process, still need use above-mentioned polymerization temperature, because ageing is carried out and is contained in the polymerization in polymerization process.The temperature of ageing process need remain on fixed level (being preferably the temperature that dropwise adds when finishing) or it can change when the time period of ageing process.Therefore, polymerization process refers to the summation of the above-mentioned total process+ageing process that dropwise adds and refers to that first ends institute's elapsed time when playing the ageing end when dropwise adding beginning.
In addition, in the production method of (methyl) of the present invention acrylic acid polymer, be aggregated under the above-mentioned acidic conditions and carry out (in the polymerization process pH of reaction soln under 25 ℃, drop in the 1-6 scope and the degree of neutralization in the polymerization process drops in the 1-25mol% scope).Therefore, the degree of neutralization of (methyl) acrylic acid polymer that generates (final degree of neutralization) can pass through post-treating method, randomly after polymerization stops, suitably adds required alkaline constituents, regulates within the limits prescribed.
Therefore above-mentioned final degree of neutralization, does not need to limit especially with using kind different and different.It can be set in the scope of very wide 1-100mol%.When polymkeric substance as for example, when declaring to be used to nurse the detergent builder of slightly acidic washing composition of baring skin, polymkeric substance can its acid state originally uses and need not to neutralize in advance.When it was used for neutral detergent or alkalis, it can pass through post-treating method before use, is neutralized to the degree of neutralization that is not less than 90mol% with alkaline constituents.Especially, when polymkeric substance used as acidic substance, final degree of neutralization was preferably in the scope of 1-75mol%, more preferably in the scope of 5-70mol%.When polymkeric substance used as neutrality or alkaline matter, final degree of neutralization was preferably in the scope of 75-100mol%, more preferably in the scope of 85-99mol%.When if polymkeric substance uses as neutrality or alkaline matter, final degree of neutralization surpasses 99mol%, and this high value may cause adding lustre to of aqueous solutions of polymers.
As the example of above-mentioned alkaline constituents, can quote from has alkali metal hydroxide such as sodium hydroxide and potassium hydroxide, alkaline earth metal hydroxides such as calcium hydroxide and magnesium hydroxide and organic amine such as ammonia, monoethanolamine, diethanolamine, and trolamine in this.These alkaline constituentses can use separately or use with two or more member's bonded forms.
Explanation in passing, in neutralization fully that will be by traditional method or the part and gained (methyl) acrylic acid polymer to be used for softening processing be not impossible to set its final degree of neutralization.But this moment, the softening processing that is increased can cause the complicated of production process and increase production cost, and as consequence, its application is restricted.
When polymkeric substance uses with its original acid state without neutralization,, surround in the atmosphere of reactive system and might contain deleterious sulfurous gas (SO because reactive system is in acid state natch 2Gas).At this moment, recommend in system, to introduce as the superoxide of hydrogen peroxide and decompose sulfurous gas or air or nitrogen are blasted system and sulfurous gas is discharged system.
(methyl) of the present invention acrylic acid polymer can pass through interrupter method or continuous processing production.
The production method of (methyl) of the present invention acrylic acid polymer, as mentioned above, be characterised in that one or more the initiator of combination that uses persulphate and bisulfite, wherein based on the persulphate of a weight part, the scope of the amount of bisulfite is the 0.5-5 weight part, add polymerization reaction system persulphate and bisulfite total weight range be every mole of monomer 2-20 gram, and the polymeric reaction temperature scope is 25-99 ℃.Here, polyreaction is preferably carried out (in the polymerization process pH of reaction soln drop in the 1-6 scope and the degree of neutralization in the polymerization process drops in the 1-25mol% scope) under 25 ℃ under acidic conditions, and each dropwise adition process that dropwise adds component is regulated simultaneously continuously.The solid constituent concentration of polymkeric substance was not less than the weight-average molecular weight of the 35 weight % and the polymkeric substance that generates in the 2000-20000 scope when preferably, polyreaction stopped.As long as the weight-average molecular weight of (methyl) acrylic acid polymer that is generated is in above-mentioned scope, the amount that adds the initiator of polymerization reaction system can significantly reduce.This true benefit is to reduce cost, stop the generation of impurity in the discharging of sulfurous gas and the production process efficiently and effectively, and produce efficiently then and can significantly and effectively now state performance such as polymolecularity in high-level following table, (methyl) acrylic acid polymer of high sequestering power and high antigelation performance.That is, can high quality and low cost produce and to be advantageously used in the mineral dye dispersion agent, the polymkeric substance of washing agent and detergent builder.In addition, add the increase of amount of the initiator of polymerization reaction system by remarkable inhibition, can realize the reduction of cost.
The purposes of (methyl) of the present invention acrylic acid polymer of having found comprises, for example, contains water dispersant (comprising the dispersing of pigments agent), washing agent (scale suppression agent), detergent builder and use the washing composition of this auxiliary agent.Its purposes does not need to be confined to this and can comprise different widely purposes.This polymkeric substance can be used as, for example, and metal ion wedding agent, thickening material and various binding agent.
The water dispersant characteristics that contain of the present invention are to contain (methyl) acrylic acid polymer (product that comprises as mentioned above (methyl) acrylic acid polymer purifying).Because the content of impurity significantly reduces in (methyl) acrylic acid polymer, the low-molecular-weight water dispersant that contains is owing to (methyl) provided by the present invention acrylic acid polymer institute inherent performance, can show outstanding dispersiveness, sequestering power and antigelation performance.The present invention also provides the water dispersant that contains with high unusually quality and performance and excellent in stability, and makes it neither because of long storage makes downgrade, also can not be settled out impurity when low tempertaure storage.
Contain in the water dispersant in the present invention, remove the component of above-mentioned (methyl) acrylic acid polymer in the composition and qualification especially of proportion in combination.Above-mentioned such component and the ratio in composition thereof can suitably be used (use) in the scope that does not influence operation of the present invention and effect, it is based on being effectively applied to each component and their ratios in composition that tradition contains water dispersant.
Washing agent characteristics of the present invention are that it contains (methyl) acrylic acid polymer (product that comprises as mentioned above (methyl) acrylic acid polymer purifying).Because the content of impurity significantly reduces in (methyl) acrylic acid polymer, low-molecular-weight water-soluble washing agent is because (methyl) provided by the present invention acrylic acid polymer institute inherent performance, can show outstanding dispersiveness, sequestering power and antigelation performance.The present invention also provides has the unusual high quality and the washing agent of performance and excellent in stability, and makes it neither because of long storage makes downgrade, also can not be settled out impurity when low tempertaure storage.
In washing agent of the present invention, remove the component of above-mentioned (methyl) acrylic acid polymer in the composition and qualification especially of proportion in combination.Above-mentioned such component and the ratio in composition thereof can suitably be used (use) in the scope that does not influence operation of the present invention and effect, it is based on the each component that is effectively applied to traditional washing agent and their ratios in composition.
Detergent builder characteristics of the present invention are that it contains (methyl) acrylic acid polymer (product that comprises as mentioned above (methyl) acrylic acid polymer purifying).Because the content of impurity significantly reduces in (methyl) acrylic acid polymer, low-molecular-weight water soluble detergent builder is because (methyl) provided by the present invention acrylic acid polymer institute inherent performance, can show outstanding dispersiveness, sequestering power and antigelation performance.Therefore, detergent builder, when using, its article that prevent to clean are again by soiled excellent performance.The present invention also provides has the unusual high quality and the detergent builder of performance and excellent in stability, and makes it neither because of long storage makes downgrade, also can not be settled out impurity when low tempertaure storage.
In detergent builder of the present invention, remove the component of above-mentioned (methyl) acrylic acid polymer in the composition and qualification especially of proportion in combination.Above-mentioned such component and the ratio in composition thereof can suitably be used (use) in the scope that does not influence operation of the present invention and effect, it is based on the each component that is effectively applied to conventional washing agent builder and their ratios in composition.
Washing composition characteristics of the present invention are that it contains (methyl) acrylic acid polymer (product that comprises as mentioned above (methyl) acrylic acid polymer purifying).Because the content of impurity significantly reduces in (methyl) acrylic acid polymer, low-molecular-weight water soluble detergent is because (methyl) provided by the present invention acrylic acid polymer institute inherent performance, can show outstanding dispersiveness, sequestering power and antigelation performance.The present invention also provides has the unusual high quality and the washing composition of performance and excellent in stability, and makes it neither because of long storage makes downgrade, also can not be settled out impurity when low tempertaure storage.
The scope that washing composition of the present invention preferably contains the ratio of the present invention's (methyl) acrylic acid polymer is the 1-20 weight % based on the washing composition gross weight, and tensio-active agent, and its ratio is the 5-70 weight % based on the washing composition gross weight.Choose wantonly, the ratio that wherein can also be no more than 5 weight % is introduced enzyme.
The quantity not sufficient 1 weight % of contained in the washing composition if (methyl) acrylic acid polymer, this low value make add material effect can not as desiredly show.If its ratio is higher than 20 weight %, this high value will make the effect of admixture not connect and finally to damage its economy with the reinforcement that washing is renderd a service.If the amount as the tensio-active agent of a main component of washing composition departs from above-mentioned scope, it is influenced and may cause detergent washing to be renderd a service being subjected to negative impact that this departs from the balance that may cause between tensio-active agent and other components.The contribution that enzyme is introduced is to improve washing and renders a service.But if the amount of the enzyme of introducing surpasses 5 weight %, this high value will make the effect of increase can not show and finally damage its economy.
At least a anion surfactant that is selected from of tensio-active agent used herein, nonionogenic tenside, amphoterics, and cats product.Anion surfactant does not limit especially.Can quote from this example of spendable anion surfactant has, alkylbenzene sulfonate, alkyl or alkenyl sulfuric acid ether, alkyl or alkenyl vitriol, alkene sulfonate, alpha-sulfonated fatty acid or ester, alkane sulfonate, saturated or unsaturated fatty acid salt, the alkyl or alkenyl ether carboxylate, amino acid surfactant, N-amido acids tensio-active agent and alkyl or alkenyl phosphoric acid ester or its salt.
Nonionogenic tenside does not limit especially.Can quote from this example of spendable nonionogenic tenside polyoxyalkylenes alkyl or alkenyl ether, polyalkylene glycol alkyl phenyl ether are arranged, higher fatty acid alkyl alcoholamine or its oxirane adducts, sucrose fatty ester, alkyl is joined sugar, fatty mono glyceride, and alkyl amine oxide.
Amphoterics does not limit especially.Available is carboxylic acid type or sultaine type amphoterics herein.
Cats product does not limit especially.Available is herein, for example, and quaternary ammonium salt.
The enzyme that available can be introduced in the washing composition among the present invention has proteolytic enzyme, lipase, and Mierocrystalline cellulose.
In addition, washing composition of the present invention, when needs, can be to wherein introducing the following component that is usually used in washing composition, alkaline auxiliary lotion as is known, the inner complex washing assistant, anti-adhesive agent is again released finish, anti-color transfer agent, tenderizer, fluorescent agent, SYNTHETIC OPTICAL WHITNER, bleaching assistant, and spices.Also can introduce molecular sieve.
As the alkaline auxiliary lotion, can use silicate, carbonate and vitriol.As the inner complex washing assistant, can choose the use diglycollic acid wantonly, hydroxycarboxylate, EDTA (ethylenediamine tetraacetic acid (EDTA)), DTPA (diethylenetriamine pentaacetic acid), and citric acid.In addition, can use the polycarboxylate-type polymkeric substance, its ratio should not exert an influence to effect of the present invention yet.
Form when the mode of adding above-mentioned (methyl) acrylic acid polymer depends on the washing composition sale in washing composition of the present invention (as, for example, liquid or solid-state), and do not need to limit especially.The polymkeric substance that obtains with aqueous solution form after the polymerization can be introduced washing composition without the form that changes.In addition, the polymkeric substance that obtains with the aqueous solution form distillation dehydration that can carry out is to a certain degree handled to be used for washing composition to concentrate attitude.Alternatively, can introduce in the washing composition being hardened to the exsiccant polymkeric substance.
Above-mentioned washing composition comprises that also a kind of function of component wherein is reinforced washing composition such as the bleach detergent to finish specific purpose uniquely, at textile industry and other industrial industrial detergents and hard facial washing composition except that household synthetic detergent.
The 3rd aspect of the present invention is at unsaturated alkylene glycol copolymer, wherein multipolymer originates from the copolymerization of (methyl) propylene type monomer A and unsaturated polyalkylene glycol type monomers B, multipolymer contains rhodanine on its end group, and the amount of the element sulphur introduced of S value representation wherein, it defines with following formula: S=(content of S in the polymkeric substance)/(total amount of S) * 100, this value is not less than 3.Polymerization in the aqueous solution generates unsaturated alkylene glycol copolymer by (methyl) propylene type monomer A and unsaturated polyalkylene glycol type monomers B.Randomly, can participate in copolymerization with monoene key (monoethylenically) the unsaturated monomer C of monomer A and monomers B copolymerization.Unsaturated alkylene glycol copolymer of the present invention is a water-soluble polymers, has lower molecular weight, is associated with rhodanine and antigelation performance on its end group, dispersiveness and sequestering power excellence.In specialized range, unsaturated alkylene glycol copolymer is had be not less than the requirement of 3 S value (being element sulphur introducing amount) to be met by controlled polymerization temperature and degree of neutralization in process of production.By this control, the discharging of sulfurous gas and the generation of impurity are reduced in a large number.Have the unsaturated alkylene glycol copolymer that is not less than 3 S value (i.e. the amount of the element sulphur of being introduced in process of production), have low-down foreign matter content and the reduction of the quality that caused by impurity is suppressed to low-down level.This multipolymer because it is suppressed to low level with aqueous solution form sedimentary impurity in the low tempertaure storage process, is water white and its tone is better than traditional unsaturated alkylene glycol copolymer.Therefore, can realize the further lifting of the quality of this polymkeric substance.
Used term " rhodanine " refers to contain the acidic-group and the salt thereof of sulphur atom and Sauerstoffatom in this specification sheets.As the example of rhodanine, can quote from having in this: derived from sulfonic acid, sulfuric acid, the group of persulfuric acid and sulfurous acid; Above-mentioned acidic group partly neutralize with basic metal or all in and gained salt; And above-mentioned acidic group with ammonia or as the organic amine of monoethanolamine or trolamine partly neutralizes or all in gained salt.
The S value, the amount of element sulphur that unsaturated alkylene glycol copolymer is introduced surpasses 3 and also preferably falls within the 3-50 scope, more preferably in the 3-30 scope.If the S value, the amount of the element sulphur of introducing, less than 3 means that the amount of initiator that polymerization is used surpasses desirable value.Therefore, this low value will cause making the formation of impurity and the discharging of sulfurous gas to be suppressed effectively, and may cause being settled out impurity in the low tempertaure storage process of the reduction of quality and multipolymer.Simultaneously, the S value, promptly the upper limit of the amount of the element sulphur of introducing does not need to limit especially.
The amount of the contained S in the term " polymer " that uses in the S value defined ", the promptly above-mentioned amount of introducing element sulphur refers to be included in the amount of the S in the unsaturated alkylene glycol copolymer.More particularly, it refers to forming the aqueous solution from the solid constituent concentration of regulating polymerization gained unsaturated alkylene glycol copolymer, removed as the dialysis process of using that remains after the LMWC of impurity and the initiator relic, it will be in hereinafter making an explanation among the embodiment, the S content in the superpolymer component that is made of unsaturated alkylene glycol copolymer that obtains.In other words, it can be considered the amount that refers to S, and it introduces the end group or the side chain of unsaturated alkylene glycol copolymer as sulfur-containing group with the sulfonic group form.Can think that in logic be included in the S component part in the used initiator, it is suitably introduced in the unsaturated alkylene glycol copolymer by polyreaction, with the S value, i.e. the increase of the amount of the element sulphur of introducing and increasing.Above-mentioned S value, i.e. the amount of the element sulphur of introducing, the term that uses in the definition " total amount of S " refers to the amount of contained whole S during the unsaturated alkylene glycol copolymer place is mutually.Do not use the amount of S in the polymer raw, but being the amount of discharging the S (sulphur component) of system with the sulfurous gas form, the reason of the total amount of S is not included in the unsaturated alkylene glycol copolymer aqueous solution, thus can not be to contain the form precipitation of S impurity in the low tempertaure storage process.
Used term " unsaturated alkylene glycol copolymer " refers to a comprehensive notion among the present invention, it has contained the aqueous solution that contains the unsaturated alkylene glycol copolymer that obtains by polymerization, above-mentioned with suitable amount to wherein having added or from wherein having shifted out solvent to regulate the aqueous solution of solid constituent concentration resemble water, by removing the water solvent in the aqueous solution and the solid matter of dried residue gained, by suitably removing the impurity in the aqueous solution that contains the unsaturated alkylene glycol copolymer that derives from polyreaction and the unsaturated alkylene glycol copolymer of purifying residue gained, to wherein having added or from wherein having shifted out water solvent to regulate the aqueous solution of solid constituent concentration, be dried to solid-state unsaturated alkylene glycol copolymer, and derive from the polymeric unsaturated alkylene glycol copolymer, it randomly contains following suitable additive, for example, shelf-stable agent (UV light absorber and oxidation inhibitor), tinting material, static inhibitor, along lubrication prescription, weighting agent, fire retardant, and whipping agent, the ratio of its introducing amount is not enough to influence unfriendly the quality of polymerization gained unsaturated alkylene glycol copolymer.Thereby unsaturated alkylene glycol copolymer of the present invention has comprised the situation that only generates the such material of pure unsaturated alkylene glycol copolymer.Therefore, unsaturated alkylene glycol copolymer of the present invention only need satisfy element sulphur that representative is introduced above amount the S value requirement and should in the widest as far as possible scope, be understood and be not limited to its title itself.It should straitly not understood (restriction) and is the solid constituent of unsaturated alkylene glycol copolymer or its aqueous solution.From simplifying the angle of production process, recommendable is directly the aqueous solution that comprises unsaturated alkylene glycol copolymer that derives from polyreaction to be used as, for example, and dispersion agent, washing agent, and detergent builder.From reducing the angle of transportation cost, recommendable is multipolymer randomly can be transported with the form of the form of solid matter rather than the bulky aqueous solution, for example work as polymkeric substance and be used as dispersion agent, when washing agent and detergent builder synthesize.From making constant product quality and making the angle of the shelf-stable of product, recommendable is that the aqueous solution that comprises unsaturated alkylene glycol copolymer that can will derive from polyreaction by removing the impurity in the aqueous solution is converted into the finished product.Thus, polymkeric substance can suitably be given such shape and composition for being fit to different purposes.Promptly, unsaturated alkylene glycol copolymer does not need to limit especially according to shape and composition, only needs to be not less than 3 by the S value that polymerization gained multipolymer satisfies with the amount of the element sulphur that representative is introduced of method (specifically describing among the embodiment hereinafter) assay determination of stipulating.
Unsaturated alkylene glycol copolymer of the present invention has and is not higher than 2, preferably is not higher than 1.5 tone (b value).Unsaturated alkylene glycol copolymer of the present invention with derive from having of conventional art yellow-brown unsaturated alkylene glycol copolymer is in a ratio of water white.When ordinary consumer (client) selected this class to be generally the washing composition of white, they usually even will consider the tone of this class washing composition.Because water white washing composition is better than those and presents yellow person on commercial value, it is highly favourable that colourless and transparent polymkeric substance is proved to be.
Unsaturated alkylene glycol copolymer of the present invention is preferably at calcium-binding capacity, specify among its embodiment that quotes from hereinafter, be not less than at 200 o'clock, satisfy degree of gelation q and be not more than 0.1 requirement, specify among its embodiment that quotes from hereinafter, satisfy above-mentioned S value simultaneously, i.e. the requirement of the amount of the element sulphur of introducing.When calcium-binding capacity less than 200 the time, Q value=(calcium-binding capacity) 2/ degree of gelation/10 5Preferably be not less than 30.So far, the polymkeric substance that has the antigelation ability in other low-molecular weight polymers has low especially molecular weight usually.That is, be the antigelation performance that obtains being fit to, need further to reduce the molecular weight that this script has had low-molecular-weight polymkeric substance.Yet for having low-molecular-weight polymkeric substance, on the end group of polymkeric substance or side chain with the sulfonic group form quantitatively thiylation group be difficult, in the time of particularly will making its amount satisfy the S value of the amount of introducing element sulphur defined above.Therefore, this polymkeric substance can not show its dispersiveness with being entirely satisfactory and detergent power is not suitable for as dispersion agent, washing agent, or detergent builder.In contrast, introduced sulfur-containing group quantitatively with the sulfonic group form on the end group of unsaturated alkylene glycol copolymer of the present invention or the side chain, particularly, its introducing amount has satisfied the S value of the amount of the above-mentioned element sulphur of introducing.Optional, it can satisfy above-mentioned q or Q value.Therefore, above-mentioned unsaturated alkylene glycol copolymer can show gratifying antigelation performance, although it has macromolecule with the traditional polymer phase ratio with antigelation performance.Need only above-mentioned S value and represent the Q value of antigelation performance to fall in the above-mentioned scope, unsaturated alkylene glycol copolymer, when being used as containing water dispersant, washing agent, or during detergent builder, can suppress gelation tendency and satisfied especially antigelation ability and the calcium-binding ability of performance of himself.Therefore, this multipolymer can be advantageously used in and contain water dispersant, washing agent, or purposes such as detergent builder.Because this multipolymer can be at the environment that uses with its original form, and under storage environment, when mixing (chemical combination), can resist the gelation tendency of himself, use the product of this multipolymer can realize that quality reaches and then the further raising of quality stability with other components.
When calcium-binding ability surpasses 200, the q value of representing degree of gelation is less than 0.1, preferably less than 0.095.When calcium-binding ability less than 200, represent the Q value of antigelation ability to be not less than 30, preferably be not less than 35, more preferably be not less than 40.If the q value is not less than 0.1, if or the Q value be not more than 30, the possible purposes of this multipolymer will be restricted owing to the antigelation scarce capacity.The high limit of the lower bound of q value or Q value does not limit especially.
For determining above-mentioned " degree of gelation, q ", can suitably use the known method that is used to measure the unsaturated alkylene glycol copolymer degree of gelation.For example, by with low concentration aqueous solution's (solid constituent concentration that for example has 1 weight %) of unsaturated alkylene glycol copolymer of the present invention with calcium chloride water together adds in the buffered soln and with its preparation test soln admixed together.By making test soln under specified temperature, keep the specified time (for example, 90 ℃ and 1 hour), measure its specific absorption at UV-light (UV) wavelength zone thereafter, can measure degree of gelation.Measure degree of gelation, describe among the embodiment that the method more specifically of q or calcium-binding capacity will be quoted from hereinafter.
The weight-average molecular weight of unsaturated alkylene glycol copolymer of the present invention, Mw is usually in the scope of 2000-100000, preferably in the 3000-50000 scope, more preferably in the 4000-20000 scope.If weight-average molecular weight is in this scope, unsaturated alkylene glycol copolymer can be significantly and is shown various performances effectively, as dispersiveness, and sequestering power and antigelation performance.Therefore, multipolymer can be used for such as dispersion agent with being more suitable for, during washing agent and detergent builder etc. are used.If the weight-average molecular weight of unsaturated alkylene glycol copolymer is lower than 2000, this low value may make dispersive ability and sequestering power can not show and limit with being entirely satisfactory the use of this polymkeric substance.On the contrary, if the weight-average molecular weight of unsaturated alkylene glycol copolymer surpasses 100000, this high value will cause the molecular weight of multipolymer very high and make it easily to show gratifying water-soluble and resistant to gelling.Contain the unsaturated alkylene glycol copolymer solid weight-average molecular weight that the aqueous solution of unsaturated alkylene glycol copolymer obtains by appropriate means with purifying polymerization gained, in fact weight-average molecular weight with contain the aqueous solution of unsaturated alkylene glycol copolymer with the polymerization gained does not show difference.Therefore, all be effective no matter with unsaturated alkylene glycol copolymer or its determination of aqueous solution weight-average molecular weight.
Be described among the embodiment that the weight-average molecular weight (Mw) of mensuration unsaturated alkylene glycol copolymer or its aqueous solution and the method for number-average molecular weight (Mn) will be quoted from hereinafter.
When (1) Mw less than 9000 the time, although with the Mw difference, the dispersity of unsaturated alkylene glycol copolymer of the present invention (Mw/Mn) is in the scope of 1.5-2.9, preferably in the scope of 1.8-2.7, more preferably in the scope of 2.0-2.5.At this moment, if dispersity is lower than 1.5, this low value makes the synthetic complexity that becomes.On the contrary, if dispersity is higher than 2.9, the component that this high value will cause having effective performance reduces, and causes the reduction of performance then, and may make unsaturated alkylene glycol copolymer can not show its dispersive ability fully satisfactorily, and possible purposes is restricted.When (2) Mw was in the 9000-20000 scope, dispersity was in the scope of 1.5-4.5, preferably in the scope of 2.0-4.0, more preferably in the scope of 2.5-3.5.At this moment, if dispersity is lower than 1.5, this low value makes the synthetic complexity that becomes.On the contrary, if dispersity is higher than 4.0, this high value will may make degradation owing to the component with effective performance reduces.
Calcium-the binding ability of unsaturated alkylene glycol copolymer of the present invention (sequestering power a kind of) can be by the decision of forming according to Mw and unsaturated alkylene glycol copolymer.If Mw in the 5000-10000 scope and multipolymer form by (methyl) the acrylic type monomer of 80 weight % and the unsaturated polyalkylene glycol type monomer of 20 weight %, its calcium-binding ability is not less than 160, preferably is not less than 180, more preferably is not less than 200.If calcium-binding ability is less than 160, this low value makes this multipolymer can't produce effective washability.Satisfied the S value requirement of the amount of representing the element sulphur of introducing, and preferably further satisfy following required condition, as the unsaturated alkylene glycol copolymer of the present invention of q value and Q value, aspect calcium-binding ability (sequestering power), be far superior to the unsaturated alkylene glycol copolymer (seeing given table 20 among the embodiment) that is proposed before the inventor.Therefore, it is advantageous that to show obviously superb sweat spot and the dirt that is bonded on the fabric are steeped, reach the spot of calcic component and the decomposition and the washing of calcareous tap water and render a service.
The degree of neutralization scope of unsaturated alkylene glycol copolymer of the present invention does not need special qualification, but can suitably be adjusted to suitable application target.It is usually in the 1-100% scope, preferably in the 20-99% scope, more preferably in the 50-95% scope.
Unsaturated alkylene glycol copolymer of the present invention is satisfying the preamble requirement aspect the S value of aforementioned representative element sulphur introducing amount, and (methyl) acrylic type monomer that can be by containing 30-99 weight % and unsaturated polyalkylene glycol type monomer combination polymerization in the aqueous solution of 1-70 weight % make.If desired, this multipolymer can additionally use 0-60 weight % water miscible can with the monoethylenically unsaturated monomer of above-mentioned monomer copolymerization.But prerequisite is (methyl) acrylic type monomer, unsaturated polyalkylene glycol type monomer and can be 100 with the gross weight % of the water-soluble monoethylenically unsaturated monomer of above-mentioned monomer copolymerization.Unsaturated alkylene glycol copolymer of the present invention preferably contains just like sulfonic sulfur-containing group and is connected to unsaturated alkylene glycol copolymer on its end group or the main chain.The satisfied as above unsaturated alkylene glycol copolymer of exclusive requirement is like this modified with sulfonic group form thiylation group on end group or its side chain.Therefore, although the polymer phase molecular weight higher than having that this polymkeric substance and tradition have the antigelation performance, it demonstrates the better antigelation performance of more above-mentioned traditional polymer.In addition, because this polymeric impurities content is little, it can form excellent low-molecular weight water-soluble polymer, and it is dispersed efficiently with polymkeric substance institute inherent, and sequestering power and the performance of antigelation performance are to greatly and not sacrificing its quality.Therefore, this polymkeric substance can compatibly be applied to following application such as dispersion agent, washing agent, and detergent builder.Unsaturated alkylene glycol copolymer of the present invention is by containing the unsaturated polyalkylene glycol type monomer combination polymkeric substance that polymerization makes in the aqueous solution of 30-99 weight % (methyl) acrylic type monomer and 1-70 weight %, and can not modify with sulfonic group form thiylation group on end group or its main chain.As long as multipolymer has satisfied the exclusive requirement that the S value of element sulphur amount is introduced in above-mentioned representative, it just can show operation of the present invention and effect.As toxilic acid, fumaric acid, methylene-succinic acid, 2-hydroxyethyl (methyl) acrylic copolymer and make the monomeric multipolymer of monomer C (it will specifically describe hereinafter) with note, the aqueous solution of such unsaturated alkylene glycol copolymer also is contained among the present invention, only needs it to satisfy the exclusive requirement that the S value of element sulphur amount is introduced in above-mentioned representative.
The existing low-molecular weight water-soluble polymer that is used for dispersion agent and washing agent, its weight-average molecular weight was not less than 1000 o'clock, and its antigelation performance promotes with the reduction of water-soluble polymers molecular weight, and promptly weight-average molecular weight is more near about 1000.Its sequestering power promotes with the weight-average molecular weight rising of this water-soluble polymers.Therefore, the traditional water soluble polymer makes three performances, that is, dispersiveness, sequestering power and antigelation performance, meet difficulty in lifting aspect simultaneously.
In contrast, as above-mentioned (methyl) the acrylic type monomer of 30-99 weight % and the unsaturated polyalkylene glycol type monomer of 1-70 weight % of containing, and the optional monomeric monomer polymkeric substance that polymerization in the aqueous solution forms of the water-soluble unsaturated monoene key of 0-60 weight %, and have with the sulfonic group form and be coupled to sulfur-containing group on its end group or the main chain, and satisfied the unsaturated alkylene glycol copolymer of exclusive requirement that the S value of element sulphur amount is introduced in above-mentioned representative, although have relatively large weight-average molecular weight, still have excellent dispersiveness and antigelation performance, reason is that it has with the sulfonic group form and is coupled to sulfur-containing group on polymer terminal group or the side chain.For big weight-average molecular weight, its antigelation performance is highly satisfied comparatively speaking.Therefore, the unsaturated alkylene glycol copolymer that satisfies above-mentioned these prerequisites demonstrates high dispersiveness and highly excellent antigelation performance when showing the sequestering power identical with traditional unsaturated alkylene glycol copolymer with identical weight-average molecular weight.
Unsaturated alkylene glycol copolymer of the present invention preferably has with the sulfonic group form and is connected to sulfur-containing group on its end group or the main chain, and has the antigelation performance of aforesaid height.By with the sulfonic group form sulfur-containing group being coupled to its end group, it can optimize dispersive ability and sequestering power.In addition, multipolymer can show high antigelation performance.Therefore, this unsaturated alkylene glycol copolymer can suitably be used as the dispersion agent of mineral dye, washing agent, and detergent builder.
Multipolymer is to contain (methyl) the acrylic type monomer of 30-99 weight % and the unsaturated polyalkylene glycol type monomer of 1-70 weight %, and the optional monomeric above-mentioned monomer polymkeric substance that polymerization in the aqueous solution forms of the water-soluble unsaturated monoene key of 0-60 weight %, and have the prerequisite that is coupled to the polymkeric substance of the sulfur-containing group on its end group or the side chain with the sulfonic group form and will together describe with the method for production unsaturated alkylene glycol copolymer of the present invention hereinafter.
The 4th aspect of the present invention is the production method at a kind of unsaturated alkylene glycol copolymer, it derives from the copolymerization of (methyl) acrylic type monomer A and unsaturated polyalkylene glycol type monomers B, and the combination of one or more materials of wherein respectively do for oneself persulphate and bisulfite is as initiator.
By in above-mentioned scope not only with persulphate, also bisulfite is introduced as initiator, can avoid the unsaturated alkylene glycol copolymer that generates to have unnecessary high molecular effectively, but can obtain lower molecular weight effectively.And, the unsaturated alkylene glycol copolymer that generates can be to wherein quantitatively with sulfonic group form thiylation group, especially, its amount satisfies the S value of the representative element sulphur introducing amount that above limits.The sulfur-containing group of such sulfonic group form can be introduced quantitatively, illustrates that persulphate and bisulfite finished action of evocating very satisfactorily.Therefore, polymerization reaction system do not need to add other initiator and can further reduce add the amount of initiator.As a result of, it can suppress the rising of polymerization production cost and enhance productivity.Therefore, the unsaturated alkylene glycol copolymer of being produced, can suppress with for example, the gathering of calcium metal-salt, and obtain gratifying antigelation performance.In addition, the amount of the initiator by will adding polymerization reaction system and polymeric reaction temperature control can suppress a large amount of generations of sulfurous gas and the generation of corresponding minimizing impurity within the specific limits.Therefore, can realize the further raising of quality product, the rising of polymer production cost is inhibited, and production efficiency can improve.
Monomer in the production method of the present invention need not limit especially, only needs it to contain the monomer component that can obtain unsaturated alkylene glycol copolymer by polymerization.Though it need contain (methyl) acrylic type monomer (below be sometimes referred to as " monomer A ") and unsaturated polyalkylene glycol type monomer (below be sometimes referred to as " monomers B ") at least, but optional, its can contain can with the monoethylenically unsaturated monomer of monomer A and B copolymerization (below be sometimes referred to as monomer C).Term used herein " monomer " refers to the monomer that is formed by the monomer component and does not comprise other components such as the solvent that is used for polymerization process, initiator and other additives.
As the example of above-mentioned monomer A, can quote from has vinylformic acid in this; Methacrylic acid; (methyl) vinylformic acid by as the basic metal of sodium or potassium partially or completely in gained salt; With this acid and ammonia or as the organic amine of monoethanolamine or trolamine partially or completely in and gained salt.These monomers can use separately or use with two or more member's bonded forms.Preferably, can use vinylformic acid or vinylformic acid with regulation ratio and methacrylic acid mixing gained mixture separately.
The amount of monomer A in aforementioned monomer is in the scope of 30-99 weight %, and preferably in the scope of 40-99 weight %, more preferably in the scope of 50-99 weight %, it is the ratio based on the monomer total amount.If the quantity not sufficient 30 weight % of monomer A wherein, the disadvantage of this low value is to make sequestering power and dispersive ability to show evenly satisfactorily.
Monomer A dissolves in solvent, and it will use in the preferably water and with the form of monomer A solution (being preferably the aqueous solution) in hereinafter specifically describing.When monomer A was used with solution (being preferably the aqueous solution) form, its concentration range was generally 10-100 weight %, preferably in 30-95 weight % scope, more preferably in 50-90 weight % scope.If the concentration less than 10 weight % of monomer A in the solution, this low value will make product concentration reduce and make the conveying of product and store complicated.On the contrary, the upper limit of this concentration does not need special qualification.This concentration can be 100 weight % (promptly wholes') monomer A (solution),, does not contain solvent fully that is.
Example as the monomers B component, can quote from having in this, to 1 mole as 3-methyl-3-butene-1-alcohol, 3-methyl-2-butene-1-alcohol, add the 1-300 mole in the unsaturated alcohol of 2-methyl-3-butene-2-alcohol or the vinyl carbinol, preferred 1-100 mole, the more preferably formed compound of the oxirane with 2-18 carbon atom of 5-50 mole.As the example of the oxirane with 2-18 carbon atom, can quote from has epoxy ethylbenzene, oxyethane, and propylene oxide in this.In other above-listed oxiranes, preferably use oxyethane and/or propylene oxide.When oxyethane and propylene oxide were used in combination, its degree of crosslinking need not limit.
If the oxyethane that is added and/or the mole number of propylene oxide are 0, effect of the present invention can not fully show.If this quantity surpasses 300, this high value will make effect of the present invention not improve and only improve the amount that adds significantly.
The amount of monomers B in aforementioned monomer is in the scope of 1-70 weight %, and preferably in the scope of 1-50 weight %, more preferably in the scope of 1-30 weight %, it is the ratio based on the monomer total amount.If the quantity not sufficient 1 weight % of monomers B wherein, the disadvantage of this low value is to make sequestering power and dispersive ability balance to show harmoniously.
Monomers B dissolves in solvent, and it will preferably use in water and with the form of monomers B solution (being preferably the aqueous solution) in hereinafter specifically describing.When monomers B was used with solution (being preferably the aqueous solution) form, its concentration range was generally 10-100 weight %, preferably in 30-95 weight % scope, more preferably in 50-90 weight % scope.If the concentration less than 10 weight % of monomers B in the solution, this low value will make product concentration reduce and make the conveying of product and store complicated.On the contrary, the upper limit of this concentration does not need special qualification.This concentration can be 100 weight % (promptly wholes') monomers B (solution),, does not contain solvent fully that is.
New type water-solubility multipolymer of the present invention derives from mainly the copolymerization of the monomer component that contains (methyl) acrylic type monomer A and unsaturated polyalkylene glycol type monomers B.In the above-mentioned monomer component randomly demonomerization A and monomers B contain outward can with the monoethylenically unsaturated monomer C of monomer A and monomers B copolymerization.
Above-mentioned monoethylenically unsaturated monomer C does not limit especially.As the example of monomer C, can quote from this, but not exclusive having, vinylbenzene; Styrene sulfonic acid; Vinyl acetate; Methacrylonitrile; Methacrylamide; (methyl) methyl acrylate; (methyl) vinylformic acid ethyl ester; (methyl) butyl acrylate cores; (methyl) 2-ethylhexyl acrylate; (methyl) vinylformic acid dimethylamino ethyl ester; (methyl) vinylformic acid diethyl amino ethyl ester; Vinyl carbinol; 3-methyl-3-butene-1-alcohol; 3-methyl-2-butene-1-alcohol; 2-methyl-3-butene-1-alcohol; 3-(methyl) acryloxy-1, the 2-dihydroxypropane; 3-(methyl) acryloxy-1,2-two (gathering) oxyethylene group ether propane; 3-(methyl) acryloxy-1,2-two (gathering) oxypropylene group ether propane; 3-(methyl) acryloxy-1,2-dihydroxypropane phosphoric acid ester and monovalent metal salt thereof, divalent metal salt, ammonium salt, organic amine salt, or the list or the diester of the alkyl of itself and 1-4 carbon atom; 3-(methyl) acryloxy-1,2-dihydroxypropane sulfuric ester and monovalent metal salt thereof, divalent metal salt, ammonium salt, the ester of the alkyl of organic amine salt and itself and 1-4 carbon atom; 3-(methyl) acryloxy-2-hydroxypropanesulfonic acid and monovalent metal salt thereof, divalent metal salt, ammonium salt, the ester of the alkyl of organic amine salt and itself and 1-4 carbon atom; 3-(methyl) acryloxy-2-(gathering) oxyethylene group ether propane sulfonic acid and monovalent metal salt thereof, divalent metal salt, ammonium salt, the ester of the alkyl of organic amine salt and itself and 1-4 carbon atom; Monovalent metal salt, divalent metal salt, ammonium salt, the ester of the alkyl of organic amine salt and itself and 1-4 carbon atom; 3-(methyl) acryloxy-2-(gathering) oxypropylene group ether propane sulfonic acid and monovalent metal salt thereof, divalent metal salt, ammonium salt, the ester of the alkyl of organic amine salt and itself and 1-4 carbon atom; 3-allyloxy propane-1, the 2-glycol; 3-allyloxy propane-1,2-glycol phosphoric acid ester; 3-allyloxy propane-1,2-glycol sulphonate; 3-allyloxy propane-1,2-glycol sulfuric ester; 3-allyloxy-1,2-two (gathering) oxyethylene group ether propane; 3-allyloxy-1,2-two (gathering) oxyethylene group ether propane phosphoric acid ester; 3-allyloxy-1,2-two (gathering) oxyethylene group ether propane; 3-allyl group Oxy-1,2-two (gathering) oxyethylene group ether propane phosphoric acid ester; 3-allyl group Oxy-1,2-two (gathering) oxyethylene group ether propane sulfonic acid ester; 3-allyl group Oxy-1,2-two (gathering) oxypropylene group ether propane; 3-allyl group Oxy-1,2-two (gathering) oxypropylene group ether propane phosphoric acid ester; 3-allyl group oxygen base-2,2-two (gathering) oxypropylene group ether propane sulfonic acid ester; 6-allyl group oxygen base-hexane-1,2,3,4, the 5-amylalcohol; 6-allyl group oxygen base-hexane-1,2,3,4,5-amylalcohol phosphoric acid ester; 6-allyl group oxygen base-hexane-1,2,3,4,5-amylalcohol sulphonate; 6-allyl group oxygen base-hexane-1,2,3,4,5-penta (gathering) oxyethylene group ether hexane; 6-allyloxy-hexane-1,2,3,4,5-penta (gathering) oxypropylene group ether hexane; Vinyl sulfonic acid, allyl sulphonic acid, 3-allyloxy-2-hydroxyl-propane sulfonic acid, 3-allyloxy-2-(gathering) ethylene oxide propane sulfonic acid, 3-allyloxy-2-polyoxytrimethylene propane sulfonic acid and have sulfonic monoethylenically unsaturated monomer and its monovalent metal salt, divalent metal salt, ammonium salt, and organic amine salt, or the phosphoric acid ester of this compound or sulfuric ester and monovalent metal salt thereof, divalent metal salt, ammonium salt, and organic amine salt; Monoene key unsaturated fatty acids monocarboxylic acid is as (methyl) vinylformic acid, Ba Dousuan and .-hydroxyl acrylic; Monoene key unsaturated fatty acids monocarboxylic acid with basic metal partially or completely in and gained salt; Monoene key unsaturated fatty acids monocarboxylic acid with ammonia or as the organic amine of monoethanolamine or trolamine partially or completely in and gained salt; Monoene key unsaturated fatty acids dicarboxylic acid such as toxilic acid, fumaric acid, and methylene-succinic acid; Monoene key unsaturated fatty acids dicarboxylic acid with basic metal partially or completely in and gained salt; Monoene key unsaturated fatty acids dicarboxylic acid with ammonia or as the organic amine of monoethanolamine or trolamine partially or completely in and gained salt.
Preferably make monomer polymerization in the aqueous solution in the inventive method.The aqueous solution contains solvent, initiator and other additives.
Be used for monomer and be preferably water solvent such as water, alcohol, ethylene glycol, glycerine, or polyoxyethylene glycol at the solvent that the aqueous solution carries out the polymeric polymerization reaction system.Water is particularly preferred.These water solvents can use separately or use with two or more member's bonded form.For the solubleness of above-mentioned monomer in this solvent is improved, or suitably add organic solvent in water solvent, its ratio should not produce negative interaction to each monomer polymerization.
As the example of above-mentioned organic solvent, can quote from has lower alcohol such as methyl alcohol and ethanol in this; Acid amides such as dimethylformaldehyde; With ether such as diethyl ether and dioxane.These organic solvents can use separately or use with two or more member's bonded form.
The common scope of above-mentioned solvent load is 40-200 weight %, and preferably in 45-180 weight % scope, more preferably in 50-150 weight % scope, this value is based on monomer total amount meter.If this monomer will make molecular weight improve with quantity not sufficient 10 weight %, this low value.On the contrary, if when this quantity of solvent surpasses 200 weight %, this high value will make the concentration of the unsaturated alkylene glycol copolymer of generation reduce and may need to remove solvent for use.Most of or whole solvents should drop in the reaction vessel in the starting stage of polyreaction.Partial solvent can add (dropwise) reactive system separately in polymerization process.In addition, the monomer component, initiator component and other additives should be dissolved in the solvent in advance, and these components suitably together add (dropwise) reactive system in polymerization process.
Monomer carries out being used in the polymeric process polymerization reaction system in the aqueous solution initiator is preferably one or more combination of persulphate and bisulfite.By using initiator by this way, can obtain low-molecular weight water-soluble polymer, its antigelation performance and dispersed and sequestering power excellence, and can show operation of the present invention and effect effectively.Also introduce bisulfite by introducing persulphate in initiator system when, the unnecessary high-molecular weight in the polymkeric substance that can suppress to generate produces and can produce low-molecular-weight polymkeric substance effectively.
As the example of above-mentioned persulphate, citable have Sodium Persulfate, a Potassium Persulphate, and ammonium persulphate.As the example of bisulfite, citable have Sodium Metabisulphate 65, a potassium acid sulfite, and ammonium bisulfite 56to 70.Alternative this bisulfite of sulphite or pyrosulfite.
Add persulphate and bisulfite ratio be, based on the persulphate of a weight part, the scope of the amount of bisulfite is the 0.1-10 weight part, preferable range is the 0.5-5 weight part, more preferably scope is the 1-3 weight part.If quantity not sufficient 0.1 weight part based on the bisulfite of the persulphate of a weight part, this low value can not be brought the effect of bisulfite effectively into play, may introduce sulfonic group to the end group of polymkeric substance to satisfy the aforementioned amount of the S value of the element sulphur amount of being introduced of representing, but also the weight-average molecular weight of unsaturated alkylene glycol copolymer is increased.On the contrary, if the amount based on the bisulfite of the persulphate of a weight part surpasses 10 weight parts, the introducing amount that this high value will make the bisulfite that adds in the polymerization reaction system too much and make the effect of bisulfite can not be with share is proportional to be showed with adding, excessive bisulfite is decomposed in polymerization reaction system and generate a large amount of sulfurous gas, also can in unsaturated alkylene glycol copolymer, produce impurity in a large number, and finally reduce the quality of the unsaturated alkylene glycol copolymer that generates and make product lay up period generation contamination precipitation at low temperatures.
As the persulphate of above-mentioned initiator adding and the amount of bisulfite be, total weight range of the persulphate of initiator and bisulfite is every mole of monomer 1-30 gram, and preferable range is the 3-20 gram, and more preferably scope is the 5-15 gram.Although persulphate and bisulfite add with so little total amount, the present invention is reduced to lower level by the temperature with polyreaction, can significantly reduce the generation of impurity in the generation of sulfurous gas and the production process.Like this, the unsaturated alkylene glycol copolymer that generates is had introducing the sulfur-containing group on its end group or the side chain with the sulfonic group form, and the requirement of the S value of element sulphur amount is introduced in the representative of satisfying above definition of its amount.Its also can prevent the decline of quality of the unsaturated alkylene glycol copolymer that generates and product at low temperatures lay up period produce contamination precipitation.If the total amount of the persulphate of above-mentioned initiator and bisulfite is lower than 1 gram, this low value will finally improve the molecular weight of the polymkeric substance that generates, may make as the sulfonic group of sulfur-containing group and can not be introduced on the end group of the unsaturated alkylene glycol copolymer that generated, and make the weight-average molecular weight increase of polymkeric substance with the amount of requirement that the S value of element sulphur amount is introduced in the representative of satisfying above definition.On the contrary, surpass 30 grams if add total amount, this high value will make the persulphate of initiator and bisulfite result of use can't share is proportional to be showed with adding, and produce the such negative interaction of purity decline that makes the unsaturated alkylene glycol copolymer that generates.
Above-mentioned persulphate as one of initiator component dissolves in above-mentioned solvent, in the preferably water, and adds with the form of sulfate liquor (preferred aqueous solutions).The concentration range of the persulphate that uses with the form of persulfate solution (preferred aqueous solutions) is 1-35 weight %, and preferable range is 5-35 weight %, and more preferably scope is 10-30 weight %.If the concentration deficiency of vitriol 1 weight %, this low value make product concentration reduce the most at last and make the conveying of product and store complicated.On the contrary, if the concentration of persulphate surpasses 35 weight %, this high value may produce the precipitation of persulphate.
Bisulfite as one of initiator material dissolves in above-mentioned solvent, in the preferably water, and adds with the form of bisulfite solution (preferred aqueous solutions).The concentration range of the bisulfite that uses with the form of bisulfite solution (preferred aqueous solutions) is 10-40 weight %, and preferable range is 20-40 weight %, and more preferably scope is 30-40 weight %.If the concentration deficiency of bisulfite 10 weight %, this low value make product concentration reduce the most at last and make the conveying of product and store complicated.On the contrary, if the concentration of bisulfite surpasses 40 weight %, this high value may produce the precipitation of bisulfite.
The present invention does not get rid of the embodiment pattern of other initiators of other use (comprising chain-transfer agent).The initiator of like this other can suitably use when needs use, and its amount produces any detrimentally affect for being not enough to effect of the present invention.In the present invention, the combination of above-mentioned persulphate and bisulfite is suitable for use as initiator.But initiator does not need to be defined as especially this combination.Sulfonic group can be introduced as sulfur-containing group, and its amount satisfies the requirement of the S value of above definition, and the initiator that can produce low-molecular weight polymer in one-step polymerization can be used for the present invention.
Identical described in the production method of above-mentioned other initiators and adding mode thereof and production (methyl) acrylic acid polymer, so it will omit in the following description.
In the polymerization of aforementioned monomer, the common scope of polymerization temperature is 25-99 ℃.This polymerization temperature preferably is not less than 50 ℃, more preferably is not less than 70 ℃.Polymeric reaction temperature preferably is not higher than 95 ℃ more preferably no higher than 90 ℃.Polymerization can be carried out being lower than under 90 ℃ the temperature.This temperature range is preferably 50-95 ℃, more preferably 70-90 ℃.If polymerization temperature is lower than 25 ℃, this low value can make molecular weight increase and impurity is increased, and polymerization time is prolonged to cause production efficiency to descend.On the contrary, if polymerization temperature is higher than 99 ℃, this high value will make the bisulfite of initiator decompose and a large amount of sulfurous gas that discharges, then make and produce impurity after dissolving in sulfurous gas and polymerization in the liquid phase, need from system, to discharge sulfurous gas in addition and need in polymerization process, carry out expensive recovery and the processing of discharging sulfurous gas, and, because bisulfite is overflowed with the sulfurous gas form in the initiator, making institute add initiator can not can't reduce to show its effect and molecular weight pro rata with add-on with being entirely satisfactory.Term as used herein " polymerization temperature " refers to the temperature of reaction soln in the reactive system.
Polymerization temperature need roughly not keep on a fixed level in the whole process of polyreaction consistently.Identical about described in the production method of the information of polymerization temperature and production (methyl) acrylic acid polymer, so it will omit in the following description.
In above-mentioned monomer polymerization, the pressure of reactive system does not limit especially.Identical about described in the production method of the information of this pressure and production (methyl) acrylic acid polymer, so it will omit in the following description.
Identical about described in the production method of the information of the atmosphere in the reactive system and production (methyl) acrylic acid polymer, so it will omit in the following description.
In production method of the present invention, above-mentioned monomeric polymerization is preferably carried out under acidic conditions.Identical about described in the production method of the information of acidic conditions and production (methyl) acrylic acid polymer, so it will omit in the following description.Identical about described in the production method of the information of preferred pH and pH regulator agent and production (methyl) acrylic acid polymer, so it will omit in the following description.
The degree of neutralization of polymerization process is in the 1-25mol% scope, preferably in the 2-15mol% scope, more preferably in the 3-10mol% scope.If the not enough 1mol% of degree of neutralization, this low value may cause the amount of the sulfurous gas that discharges to increase and improve molecular weight.On the contrary, if the degree of neutralization of polymerization process surpasses 25mol%, this high value will make the chain transfer efficiency of bisulfite reduce and increase molecular weight, in the process that polymerization is carried out, increase viscosity in aqueous solution in the polymerization reaction system significantly, then the molecular weight that makes the polymkeric substance that generates unnecessarily significantly improves and can't produce low-molecular-weight polymkeric substance, the effect that reduces degree of neutralization can not be showed fully satisfactorily, and make a large amount of minimizing impurity become difficult.
The neutral method is not done special qualification.Identical about described in the production method of the information of neutral method and production (methyl) acrylic acid polymer, and it will be in omission in following description the down.
In preparing for polymerization, above-mentioned monomer, the persulphate of initiator system and bisulfite, usually be dissolved in advance in the appropriate solvent (solvent phase that is preferably used liquid when dropwise reinforced with solvent) to make monomer solution respectively with other additives, persulfate solution, bisulfite solution, and additive solution.Then, by solution is dropwise added in (water) solvent (randomly being adjusted to specified temperature) insert in advance in the molten device of reaction in the section at the appointed time constantly polymerization is carried out in the expection mode.In addition, the portion water solvent can separate and dropwise add thereafter with the solvent of inserting in advance in the reaction vessel.But production method of the present invention is not limited to such method.For the method that dropwise adds, for example, dropwise add and continuously or to be divided into a plurality of segments and to carry out discontinuously.Monomeric all or part of initially feeding mode adds (being that monomeric all or part of can be considered when polymerization begins once all dropwise adds).In addition, for the speed (the dropwise monomeric amount of Jia Ruing) that monomer dropwise adds, dropwise the operation of Jia Ruing begins can keep carrying out with constant rate of speed (fixed amount) to end from dropwise adding.In addition, dropwise the speed of Jia Ruing (the dropwise amount of monomer of Jia Ruing) can prolong change in time, and this depends on factors such as polymerization temperature.Be not that the component that all are dropwise added uses same identical speed, but each component that dropwise adds staggered mutually when stopping when making polymerization initial, or its process that dropwise adds is shortened or prolongs.Therefore, production method of the present invention allows so suitable change to avoid influencing operation of the present invention and effect.When each component dropwise adds fashionablely separately with the solution form, dropwise the solution of Jia Ruing can be heated to the level identical with the polymerization temperature of reactive system in advance.When operation like this, polymerization temperature when it need remain on steady temperature following time, will only produce little change and be easy to and regulate.
In addition, the effect of bisulfite is that the molecular weight of polyreaction starting stage greatly affects its final molecular weight.Therefore, be to reduce initial molecular weight, recommend dropwise to add in after polymerization begins 60 minutes of solution with bisulfite or its 5-20 weight %, preferably in 30 minutes, more preferably in 10 minutes.This method is will be in hereinafter specifically described occasion in the room temperature initiated polymerization is particularly effective.
For polymerization, importantly reduce polymerization temperature, suppress the discharging of sulfurous gas, and stop the generation of impurity.For this reason, all processes that dropwise adds in the polymerization process need fall within 180-600 minute scope, in the preferred 210-480 minute scope, more preferably in 240-420 minute scope.But, generate polymer properties in view of the aforementioned problem that is run in process of production and in order to improve, prolong polymerization time and can be used as an important method.If dropwise all processes of Jia Ruing is less than 180 minutes, this low value will make as the persulfate solution of initiator system adding and the effect of bisulfite solution and can not bring into play effectively, thereby make with the sulfonic group form and introduce the end group of the unsaturated alkylene glycol copolymer that generated or the requirement that the sulfur-containing group on the side chain is difficult to satisfy the S value of representing the element sulphur amount of being introduced, then make polymkeric substance obtain higher weight-average molecular weight, may produce the excessive of initiator owing to the process that dropwise adds is short in reactive system, and cause the decomposition of excessive initiator, discharge sulfurous gas, make it it and from system, overflow, and form impurity.On the contrary, if dropwise the whole process of Jia Ruing was above 600 minutes, although the polymkeric substance that generates have excellent quality owing to the discharging of sulfurous gas is suppressed, this high value will make the production efficiency of unsaturated alkylene glycol copolymer reduce and may limit the use of the polymkeric substance that produces.Term used herein " the dropwise whole process of Jia Ruing " refers to dropwise add fashionable time span till when last component that dropwise adds (being not necessarily limited to a component) dropwise adds end from first component that dropwise adds (being not necessarily limited to a component) beginning.
In the component that other dropwise add, the process that bisulfite or its solution dropwise add in polymerization process, its terminal point is led over the interval in the moment of the terminal point that dropwise adds of monomer or its solution constantly should be 1-30 minute scope, preferable range is 1-20 minute, and more preferably scope is 1-15 minute.Identical about described in the production method of the information of this process and production (methyl) acrylic acid polymer, so it will omit in the following description.
In the component that other dropwise add, the process that persulphate (solution) dropwise adds in polymerization process, its terminal point lags behind the interval in the moment of the terminal point that dropwise adds of monomer or its solution constantly should be 1-30 minute scope, preferable range is 1-20 minute, and more preferably scope is 1-15 minute.Identical about described in the production method of the information of this process and production (methyl) acrylic acid polymer, so it will omit in the following description.
Above-mentioned each component dropwise adds end, and when the polyreaction in the polymerization reaction system stops, solid constituent concentration in the aqueous solution (being the concentration of monomeric solid constituent) surpasses 35 weight % preferably in 40-70 weight % scope, more preferably in 45-65 weight % scope.Identical about described in the production method of the information of this solid constituent concentration and production (methyl) acrylic acid polymer, so it will omit in the following description.
In the production method of unsaturated alkylene glycol copolymer of the present invention, be aggregated under the above-mentioned acidic conditions and carry out (in the polymerization process pH of reaction soln under 25 ℃, drop in the 1-6 scope and the degree of neutralization in the polymerization process drops in the 1-25mol% scope).Identical about described in the production method of the information of the degree of neutralization under the acidic conditions and production (methyl) acrylic acid polymer, so it will omit in the following description.
Unsaturated alkylene glycol copolymer of the present invention can pass through interrupter method or continuous processing production.
The production method of unsaturated alkylene glycol copolymer of the present invention, be characterised in that one or more the initiator of combination that uses persulphate and bisulfite, wherein based on the persulphate of a weight part, the scope of the amount of bisulfite is the 0.1-10 weight part, adding the persulphate of polymerization reaction system and total weight range of bisulfite is every mole of monomer 1-30 gram, and the polymeric reaction temperature scope is 25-99 ℃.Here, polyreaction is preferably carried out (in the polymerization process pH of reaction soln drop in the 1-6 scope and the degree of neutralization in the polymerization process drops in the 1-25mol% scope) under 25 ℃ under acidic conditions, and each dropwise adition process that dropwise adds component is regulated simultaneously continuously.Solid constituent concentration was not less than the weight-average molecular weight of the 35 weight % and the polymkeric substance that generates in the 2000-100000 scope when preferably, polyreaction stopped.As long as the weight-average molecular weight of the unsaturated alkylene glycol copolymer that is generated is in above-mentioned scope, the amount that adds the initiator of polymerization reaction system can significantly reduce.This helps production cost, and impurity generates and carries out effectively and efficiently preventing (inhibition) in sulfur dioxide emissions and the production process.Thus, can produce unsaturated alkylene glycol copolymer effectively, it can significantly and effectively now state performance such as polymolecularity in high-level following table, high sequestering power and high antigelation performance.That is, but high efficiency, low cost produce and can be advantageously used in the mineral dye dispersion agent, the polymkeric substance of washing agent and detergent builder.In addition, the increase of the amount of the initiator by reduce adding polymerization reaction system can realize the reduction of cost.
The purposes example of the unsaturated alkylene glycol copolymer of having found of the present invention, not exclusive and can quote from comprising in this, for example, contain water dispersant (comprising lime carbonate, kaolin and dispersing of pigments agent), water conditioner, washing agent (scale suppression agent), cement additire, detergent builder (comprising liquid and powdered detergent) and use the washing composition of this auxiliary agent.This multipolymer purposes does not need to be confined to this and can comprise different widely purposes.This polymkeric substance can be used as, for example, and metal ion wedding agent, thickening material and various binding agent.
The water dispersant characteristics that contain of the present invention are to contain unsaturated alkylene glycol copolymer (comprising the product of unsaturated alkylene glycol copolymer purifying as mentioned above).Because the content of impurity significantly reduces in the unsaturated alkylene glycol copolymer, the low-molecular-weight water dispersant that contains can show unsaturated alkylene glycol copolymer institute inherent outstanding dispersiveness, sequestering power and antigelation performance veritably.The present invention also provides the water dispersant that contains with high unusually quality and performance and excellent in stability, and makes it neither because of long storage makes downgrade, also can not be settled out impurity when low tempertaure storage.
Contain in the water dispersant in the present invention, remove the component of unsaturated alkylene glycol copolymer in the composition and qualification especially of proportion in composition.This contains water dispersant can suitably use (use) in the scope that does not influence operation of the present invention and effect, it is based on being effectively applied to each component and their ratios in composition that tradition contains water dispersant.
Washing agent characteristics of the present invention are that it contains unsaturated alkylene glycol copolymer (comprising the product of unsaturated alkylene glycol copolymer purifying as mentioned above).Because the content of impurity significantly reduces in the unsaturated alkylene glycol copolymer, low-molecular-weight water-soluble washing agent is because unsaturated alkylene glycol copolymer provided by the present invention institute inherent performance, can show outstanding dispersiveness, sequestering power and antigelation performance.The present invention also provides has the unusual high quality and the washing agent of performance and excellent in stability, and makes it neither because of long storage makes downgrade, also can not be settled out impurity when low tempertaure storage.
Cement additire characteristics of the present invention are that it contains unsaturated alkylene glycol copolymer (comprising the product of unsaturated alkylene glycol copolymer purifying as mentioned above).Because the content of impurity significantly reduces in the unsaturated alkylene glycol copolymer, low-molecular-weight water-soluble cement additire is because unsaturated alkylene glycol copolymer provided by the present invention institute inherent performance, can show outstanding dispersiveness, sequestering power and antigelation performance.The present invention also provides has the unusual high quality and the cement additire of performance and excellent in stability, and makes it neither because of long storage makes downgrade, also can not be settled out impurity when low tempertaure storage.
In cement additire of the present invention, remove the component of unsaturated alkylene glycol copolymer in the composition and qualification especially of proportion in composition.This cement additire can not influence in the scope of amount of operation of the present invention and effect suitably uses (use), and it is based on the each component that is effectively applied to traditional cement additire and their ratios in composition.
Detergent builder characteristics of the present invention are that it contains unsaturated alkylene glycol copolymer (comprising the product of unsaturated alkylene glycol copolymer purifying as mentioned above).Because the content of impurity significantly reduces in the unsaturated alkylene glycol copolymer, low-molecular-weight water soluble detergent builder is because unsaturated alkylene glycol copolymer provided by the present invention institute inherent performance, can show outstanding and consistency liquid washing agent, dispersed, sequestering power and antigelation performance.Therefore, detergent builder, while actually employed, it prevents again soiled excellent performance.The present invention also provides has the unusual high quality and the detergent builder of performance and excellent in stability, and makes it neither because of long storage makes downgrade, also can not be settled out impurity when low tempertaure storage.
In detergent builder of the present invention, remove the component of unsaturated alkylene glycol copolymer in the composition and qualification especially of proportion in composition.This detergent builder can not influence in the scope of amount of operation of the present invention and effect suitably uses (use), and it is based on the each component that is effectively applied to conventional washing agent builder and their ratios in composition.
Washing composition characteristics of the present invention are that it contains unsaturated alkylene glycol copolymer (comprising the product of unsaturated alkylene glycol copolymer purifying as mentioned above).Because the content of impurity significantly reduces in the unsaturated alkylene glycol copolymer, low-molecular-weight water soluble detergent is because unsaturated alkylene glycol copolymer provided by the present invention institute inherent performance, can show outstanding dispersiveness, sequestering power and antigelation performance.The present invention also provides has the unusual high quality and the washing composition of performance and excellent in stability, and makes it neither because of long storage makes downgrade, also can not be settled out impurity when low tempertaure storage.
The scope that washing composition of the present invention preferably contains the ratio of unsaturated alkylene glycol copolymer of the present invention is the 1-20 weight % based on the washing composition gross weight, and tensio-active agent, and its ratio is the 5-70 weight % based on the washing composition gross weight.Choose wantonly, the ratio that wherein can also be no more than 5 weight % is introduced enzyme.
If the quantity not sufficient 1 weight % of contained unsaturated alkylene glycol copolymer in the washing composition, this low value make add material effect can not show.On the contrary, if its ratio is higher than 20 weight %, this high value disadvantage is and will the effect of admixture can not be connected with the reinforcement that washing is renderd a service.If the amount as the tensio-active agent of a main component of washing composition departs from above-mentioned scope, it is influenced and may cause detergent washing to be renderd a service being subjected to negative impact that this departs from the balance that may cause between tensio-active agent and other components.The contribution that enzyme is introduced is to improve washing and renders a service.But if the amount of the enzyme of introducing surpasses 5 weight %, this high value will make the effect of increase can not show and finally damage its economy.
Detergent builder of the present invention originally is used for liquid washing agent or powdered detergent.Since unsaturated alkylene glycol copolymer with will be good in the surfactant compatibility that hereinafter describes in detail, it can high-concentration raw production fluid body washing composition.True thus, can recommend unsaturated alkylene glycol copolymer of the present invention is used for the builder of liquid washing agent.
Identical about described in the production method of the information that can be used for tensio-active agent of the present invention and enzyme and production (methyl) acrylic acid polymer, so it will omit in the following description.
In addition, washing composition of the present invention can randomly contain the alkali builder therein.Identical about described in the production method of the information of introducing the alkali builder and production (methyl) acrylic acid polymer, so it will omit in the following description.
The mode of the above-mentioned unsaturated alkylene glycol copolymer of adding depends on the form (for example, liquid or solid-state) when washing composition is sold in washing composition of the present invention, and does not need to limit especially.The form of the aqueous solution after this multipolymer can polymerization be finished is introduced.In addition, it can be carried out to a certain degree processed to introduce to concentrate attitude.Alternatively, can introduce being cured to the exsiccant polymkeric substance.
This washing composition removes household synthetic detergent, comprises that also a kind of function of component wherein is reinforced washing composition such as the bleach detergent to finish specific purposes uniquely, at textile industry and other industrial industrial detergents and hard facial washing composition.
Embodiment
Now, the present invention will more specifically describe by following examples and Comparative Examples.The present invention is not in office, and where face is subject to these embodiment.Appear at symbol " % " representative " weight % " in embodiment and the Comparative Examples, unless specialize.
[for (methyl) acrylic acid polymer]
For the present invention's (methyl) acrylic acid polymer, (1-1) total amount of the amount of contained S and S and the dialysis process that is used for it is measured in the polymkeric substance, (1-2) weight-average molecular weight of polymkeric substance (Mw) and number-average molecular weight (Mn), (1-3) degree of gelation q, be used to measure the Q value of representing the antigelation ability, (1-4) be used to measure the NMR of R value, (1-5) iron concentration, (1-6) calcium-binding capacity, (1-7) amount of Pai Fang sulfurous gas, (1-8) precipitation capacity under the low temperature, (1-9) measuring method of sulfurous gas component is shown in hereinafter.
(1-1) mensuration of the total amount of the amount of contained S and S in the polymkeric substance
Polymerization gained (methyl) acrylic acid polymer with dialysis method before and after treatment, wherein the amount of S uses inductance coupled plasma (ICP) emmission spectrum to measure.Herein, the amount note work " total amount of S " of S in (methyl) acrylic acid polymer before dialysis method is handled.Dialysis method is handled the amount note of S in (methyl) acrylic acid polymer of back and is made " amount that contains S in the polymkeric substance ".Dialysis process used herein will be hereinafter to describe.
" dialysis process "
1. solid constituent concentration is that (methyl) acrylic acid polymer aqueous solution of 30 weight % makes by the water that adds appropriate amount in polymerization gained (methyl) acrylic acid polymer.In the long dialysis membrane of 40cm, place the also aqueous solution of secure seal 20g.Dialysis membrane is that the fraction molecular weight is 1000 Spectra/PorMembrane MWCO:1000 (being made by Spectrum Laboatories Inc.).The present invention can use the film that has with the roughly the same fraction molecular weight of above-mentioned film.
2. dialysis membrane is immersed the 2000g water that places 2-to rise beaker, and water is stirred by agitator.
3. stir to continue after 6 hours dialysis membrane to be taken out from beaker, take out the dialysis membrane content in the dialysis membrane outside by water after the thorough drip washing.
4. extract concentrate with vaporizer and the gained enriched material as (methyl) acrylic acid polymer dialysis treatment after sample.
As sample before (methyl) acrylic acid polymer dialysis, can use with polymerization gained (methyl) acrylic acid polymer use 1. handle as above-mentioned step after again to handle the gained enriched material with the method for step identical use vaporizer as described in 4..
(1-2) mensuration of weight-average molecular weight (Mw) and number-average molecular weight (Mn)
Weight-average molecular weight (Mw) of (methyl) acrylic acid polymer and number-average molecular weight (Mn) are measured by gel permeation chromatography (GPC).As the sample of this mensuration, can use dialysis process (1) section step 1. described in polymerization gained (methyl) acrylic acid polymer without the form that changes.Used instrument and test condition are as described below.
The used post of GPC is made by Tosoh K.K, sells with the trade mark of G-3000PWXL.
The moving phase of GPC is for to be diluted to gross weight be 5000 grams and obtained aqueous solution filtered the aqueous solution that the filtering membrane of 0.45 μ m makes with purified water with 34.5 gram disodium hydrogen phosphates and 46.2 gram SODIUM PHOSPHATE, MONOBASIC (being chemical reagent-grade).
Detector make for Waters Corp. and with " Model 481type " transmitter that the product code name is sold, used detection wavelength is UV:214nm.
Used pump is Hitachi, and Ltd. makes, and uses trade mark L-7110 to sell.
The moving phase flow rate is fixed in 0.5 ml/min and temperature is 35 ℃.Calibration curve derives from the sodium polyacrylate standard model that SowaKagaku K.K makes.
(1-3) degree of gelation, q and represent the mensuration of the Q value of antigelation ability
For measuring degree of gelation, preparation borate buffer solution, calcium chloride water and 1% aqueous solutions of polymers.The preparation method of borate buffer solution restrains boric acid with purified water with 7.42, and 1.75 gram sodium-chlor and 7.63 grams, ten water Sodium Tetraboratees are diluted to the gross weights of 1000 grams.The preparation method of calcium chloride water is for being diluted to 0.735 gram Calcium dichloride dihydrate with purified water the gross weight of 2500 grams.The preparation method of above-mentioned 1% aqueous solutions of polymers for the water that is fit to dialysis process (1) section step 1. described in polymerization gained (methyl) acrylic acid polymer be diluted to the solid ingredient concentration of 1 weight %.
Then, volume is to be injected into above-mentioned solution in the high beaker of 500ml, its with specified amount in accordance with regulations order add.Described regulation order and specified amount are: inject the 250ml pure water in the beaker earlier, second step was the 10ml borate buffer solution, and the 3rd step was the aqueous solutions of polymers of 5ml 1%, was the 250ml calcium chloride water at last.
By will mixing with the solution that said sequence adds in the beaker, but contained polymkeric substance gelling and the gained mixing solutions is used as test soln in 1% the aqueous solutions of polymers.The high beaker that test soln is housed is plugged and is that 90 ℃ constant temperature was placed one hour in molten setting in advance.After past one hour, test soln is transferred in the dark quartz cell of 5cm immediately and tests its specific absorption, a, and used UV wavelength is 380nm.
Respectively,, prepare a blank solution, but substitute the 250ml calcium chloride water with the 250ml pure water with four components same as described above by the preparation process identical with above-mentioned test soln, that is, above-mentioned four components from one of.The treatment process of blank solution is identical with above-mentioned test soln, and measures its specific absorption (blank value) under UV wavelength 380nm, b.Degree of gelation, q calculates by formula a-b, and wherein a represents specific absorption and b represents blank value.
Represent the Q value of antigelation ability to calculate: Q=degree of gelation * 10 according to following formula 5/ Mw uses and measures the weight-average molecular weight income value described in described degree of gelation and above (2).
(1-4) be used to measure the R value 1H-NMR
Instrument: Varian Corp. produce with trade(brand)name " Gemini 2000 (200MHz) " product sold.
Solvent: D 2O
Resonant frequency: 199.93MHz
The convertible probe of probe: 5-mm
Observing nuclear: proton
Test condition: 90 degree pulses, 10 microseconds.(with 45 degree pulse irradiations)
Waiting time: 1.254 seconds
Integration number: 16
Temperature: room temperature
Sample preparation methods: by 0.1 gram (methyl) acrylic acid polymer (its solvent component removes fully by vacuum-drying) is used D 2O is diluted to gross weight 1.0 grams and complete dissolve polymer makes a duplicate samples.
(1-5) iron concentration is measured
Polymerization gained (methyl) acrylic acid polymer is by ICP emission spectrographic determination iron concentration.
(1-6) calcium-binding capacity is measured
At a volume is in the beaker of 100ml, places the calcium chloride water of 50 gram 0.001mol/L.In this solution, add 10mg poly-(methyl) vinylformic acid of simmer down to solid constituent.Then with the dilution sodium hydroxide solution with this aqueous solution pH regulator to the scope of 9-11.Then, this solution is continued stirring and also under agitation in this solution, add the Klorvess Liquid of 1ml 4mol/L as the calcium ion electrode stablizer.
Gained solution is measured its free calcium ion and is converted into lime carbonate by calculating poly-(methyl) acrylate of every gram to what milligram calcium ions should be arranged with ion analyser (Orion K.K. makes and sells with commercial disignation " EA920model ") and calcium ion electrode (OrionK.K. makes and sells with commercial disignation " 93-20model "), it has experienced chelating (calcium-binding capacity, sequestering power a kind of).The unit of a kind of calcium-binding capacity of sequestering power is " mg CaCO 3/ g ".
(1-7) amount of Pai Fang sulfurous gas (gas volume)
The amount of the gas of discharging was measured with the aerometer (Shinagawa K.K. makes and sells with " Dry Test Gas Meter Model DC-2 " registered trademark) that is attached on the reflux exchanger between the polymerization zero hour and polymerization stopped constantly.
(1-8) precipitation capacity under the low temperature
1. in the 50ml bottle of internal diameter 32mm, the 50 given aqueous solutions of polymers of gram (polymkeric substance of embodiment or the polymkeric substance of Comparative Examples) are cooled to 0 ℃ with threaded cap.
2. with minor N a 2SO 4Monocrystalline adds in the solution and in 0 ℃ as crystal seed to be placed 12 hours.
3. evaluation criteria: crystal settling be no less than the liquid levels height half be decided to be " many " and the crystal settling that is less than this amount is decided to be " on a small quantity ".
(1-9) method for quantitatively determining of content of sulfur dioxide
Made solution (below be called " solution 2. ") in 5 minutes by 20 gram polymkeric substance (polymkeric substance of embodiment or the polymkeric substance of the Comparative Examples) aqueous solution and 1 are restrained about 1% aqueous hydrogen peroxide solution (below be called " solution 1. ") mixes and they are stirred together.Then, measure solution concentration of hydrogen peroxide 2. with following method.
In the Meyer of volume 300ml flask, place 2 gram potassiumiodides and also stir with the 100 gram pure water that add wherein with magnetic stirring apparatus.When potassiumiodide dissolves fully, in obtained aqueous solution, add
Figure C20061009565300561
(9mol/ (dm) 3) sulfuric acid.2. gained solution and the about 18-20 gram solution that adds wherein stirred 5 minutes under the state that is covered by light-shielding sheet.The gained mixture is with the Sulfothiorine titration of 0.1M.Titration continues to solution lentamente and presents glassy yellow.This solution and adding wherein
Figure C20061009565300562
Amidin is titration to iodamylum color disappear (A ml) together.Blank sample (making) titration in the same manner as described above (B ml) by in above-mentioned steps, saving solution adding 2..Solution concentration of hydrogen peroxide 2. calculates according to following formula.Solution concentration of hydrogen peroxide 1. can carry out similar calculating.
Concentration of hydrogen peroxide (%)=[(A-B) * 0.1M Sulfothiorine coefficient * 17]/(solution 1. or solution add-on (g) 2.)
Then calculate the hydrogen peroxide that solution is consumed in 2..
Concentration of hydrogen peroxide (%)=[solution is the concentration of hydrogen peroxide (%) 1.] that solution is consumed in 2. * [solution 1. (g)/solution 2. (g)-1]
Add the sulfurous gas component of solution in 2. and calculate according to following formula and be reduced to bisulfite.
Add the sulfurous gas component (g) of solution in 2.=(concentration of hydrogen peroxide (%) that solution is consumed in 2.)/100 * [add solution amount (g) 2.] * 108/34.
At last, whole aqueous solutions of polymers, promptly in the aggregation container in all aqueous solutions of polymers content of sulfur dioxide (g) calculate according to following formula and be reduced to bisulfite.
Amount of sulfur dioxide in the whole aqueous solutions of polymers (g)=(add solution 2. in heavy sulfurous acid content (g)) * { aqueous solutions of polymers total amount (g) }/[{ institute adds solution amount (g) 2. } * { (solution is the amount (g) of middle aqueous solutions of polymers 2.)/(solution is (g) 2.) }]
Embodiment 1
2.5 liters of the volumes of making at SUS have been installed in the separable flask of reflux exchanger and agitator and have been placed 156.5g pure water (first batch of reinforced) and be heated to 90 ℃ under whipped state.
Then, under being constant at about 90 ℃ of temperature and in the polymerization reaction system that continues to stir, dropwise add the acrylic acid aqueous solution (being designated hereinafter simply as " 80%AA ") of 427.5g (4.75mol) 80% by independently dripping nozzle separately, 63.5g (0.25mol) the 37% sodium acrylate aqueous solution (being designated hereinafter simply as " 37%SA "), 66.7g (2.0g/mol, be reduced to respect to adding amount of monomer (wherein, refer to all add monomeric total amounts at this term " add amount of monomer "; Hereinafter its implication is similar)) 15% sodium persulfate aqueous solution (being designated hereinafter simply as " 15%NaPS "), and 71.4g (5.0g/mol is reduced to respect to amount of monomer adding) the 35% Sodium Metabisulphate 65 aqueous solution (being designated hereinafter simply as " 35%SBS ").Dropwise the time of Jia Ruing is 80%AA, and 37%SA and 35%SBS respectively did for oneself 300 minutes, and 15%NaPS is 310 minutes.Dropwise in the adition process, relevant component adds continuously with the fixed drop rate separately.
After dropwise add stopping, reaction soln kept 30 minutes so that ageing of solution and finish polymerization at 90 ℃.After polymerization was finished, reaction soln was cooled and neutralizes by stirring down to the aqueous sodium hydroxide solution (being designated hereinafter simply as " 48%NaOH ") that wherein dropwise adds 366.7g (4.40mol) 48% lentamente.Thus, obtaining solids concn is that 45 weight % and final degree of neutralization are the aqueous solution that contains sodium polyacrylate (below be referred to as " polymkeric substance (1) ") of 93mol%.Polymerizing condition brief summary used herein is in following table 1.
Resulting polymers (1) is measured its molecular weight thus, S value, R value, Q value, iron concentration, calcium-binding capacity, precipitation capacity under gas volume and the low temperature.The results are shown in table 11.
Embodiment 2-14
The polymkeric substance of described embodiment obtains by embodiment 1 step.The condition brief summary of these polymkeric substance is in following table 1 and table 2.
Molecular weight is separately measured in resulting polymers (2)-(14) thus, S value, R value, Q value, iron concentration, calcium-binding capacity, precipitation capacity under gas volume and the low temperature.The results are shown in table 11.
Table 1
Figure C20061009565300591
Table 2
Figure C20061009565300601
Embodiment 15-17
The polymkeric substance of described embodiment obtains by embodiment 1 step, dropwise adds 80%AA in beginning simultaneously, adds the SBS of 7.1g (0.5g/mol is reduced to respect to amount of polymers adding) 35% before the 37%SA, 35%SBS and 15%NaPS immediately fast.The condition brief summary of these polymkeric substance is in following table 3.
Resulting polymers (15)-(17) are measured its molecular weight separately thus, S value, R value, Q value, iron concentration, calcium-binding capacity, precipitation capacity under gas volume and the low temperature.The results are shown in table 11.
Table 3
Figure C20061009565300621
Embodiment 18
2.5 liters of the volumes of making at SUS have been installed in the separable flask of reflux exchanger and agitator and have been placed 137.0g pure water (first batch of reinforced) and be heated to 30 ℃ under whipped state.Then, stir down to the SBS that wherein adds 7.1g (0.5g/mol is reduced to respect to amount of monomer adding) 35% fast.In gained polymerization reaction system like this, dropwise add 405.0g (4.50mol) 80%AA by independently dripping nozzle separately, 127.0g (0.50mol) 37%SA, 66.7g (2.0g/mol, be reduced to respect to amount of monomer adding) 15%NaPS, and 85.7g (6.0g/mol is reduced to respect to amount of monomer adding) 35%SBS.Dropwise the time of Jia Ruing is 80%AA, and 37%SA and 35%SBS respectively did for oneself 240 minutes, and 15%NaPS is 250 minutes.Polymerization temperature raises in polyreaction speed with 1 ℃ of per minute after 30 ℃ of initiations, and is constant at 90 ℃ after 60 minutes after the polymerization initiation beginning.Dropwise in the adition process, relevant component adds continuously with the fixed drop rate separately.
After dropwise add stopping, reaction soln kept 30 minutes so that ageing of solution and finish polymerization at 90 ℃.After polymerization was finished, reaction soln was cooled and neutralizes by stirring down to wherein dropwise adding 366.7g (4.40mol) 48%NaOH lentamente.Thus, obtaining solids concn is that 45 weight % and final degree of neutralization are the aqueous solution that contains sodium polyacrylate (below be referred to as " polymkeric substance (18) ") of 93mol%.Polymerizing condition brief summary used herein is in following table 4.
Resulting polymers (18) is measured its molecular weight thus, S value, R value, Q value, iron concentration, calcium-binding capacity, precipitation capacity under gas volume and the low temperature.The results are shown in table 11.
Embodiment 19
2.5 liters of the volumes of making at SUS have been installed in the separable flask of reflux exchanger and agitator and have been placed 154.0g pure water (first batch of reinforced) and be heated to 30 ℃ under whipped state.In gained polymerization reaction system like this, and keep continuing to stir down, dropwise add 427.5g (4.75mol) 80%AA by independently dripping nozzle separately, 63.5g (0.25mol) 37%SA, 66.7g (2.0g/mol, be reduced to respect to amount of monomer adding) 15%NaPS, and 85.7g (6.0g/mol is reduced to respect to amount of monomer adding) 35%SBS.Dropwise the time of Jia Ruing is 80%AA, and 37%SA and 35%SBS respectively did for oneself 300 minutes, and 15%NaPS is 310 minutes.But, SBS for 35%, it begins dropwise to add altogether in back 10 minutes 7.1g (0.5g/mol is reduced to respect to amount of monomer adding) in polymerization, in thereafter 290 minutes, add 78.6g (5.5g/mol is reduced to respect to amount of monomer adding) altogether.Polymerization temperature raises in polyreaction speed with 1 ℃ of per minute after 30 ℃ of initiations, and is constant at 90 ℃ after 60 minutes after the polymerization initiation beginning.Dropwise in the adition process, relevant component adds continuously with the fixed drop rate separately.But, the SBS for 35%, polymerization begin in back 10 minutes the speed (fixed value) that dropwise adds with remaining 290 minutes in dropwise the speed (fixed value) of adding is different.
After dropwise add stopping, reaction soln kept 30 minutes so that ageing of solution and finish polymerization at 90 ℃.After polymerization was finished, reaction soln was cooled and neutralizes to wherein dropwise adding 366.7g (4.40mol) 48%NaOH lentamente by continuing to stir down.Thus, obtaining solids concn is that 45 weight % and final degree of neutralization are the aqueous solution that contains sodium polyacrylate (below be referred to as " polymkeric substance (19) ") of 93mol%.Polymerizing condition brief summary used herein is in following table 4.
Resulting polymers (19) is measured its molecular weight thus, S value, R value, Q value, iron concentration, calcium-binding capacity, precipitation capacity under gas volume and the low temperature.The results are shown in table 11.
Embodiment 20
Step according to example 19 obtains a polymkeric substance (hereinafter referred to as " polymkeric substance 20 ").The condition brief summary of this polymkeric substance is in following table 4.
Resulting polymers (20) is measured its molecular weight thus, S value, R value, Q value, iron concentration, calcium-binding capacity, precipitation capacity under gas volume and the low temperature.The results are shown in table 11.
Embodiment 21
2.5 liters of the volumes of making at SUS have been installed and have been placed 154.0g pure water (first batch of reinforced) in the separable flask of reflux exchanger and agitator and stir, and feed nitrogen to the speed with 1 liter/minute wherein, and aeration time is 30 minutes, and together is heated to 30 ℃.In gained polymerization reaction system like this, and keep continuing to stir down, dropwise add 427.5g (4.75mol) 80%AA by independently dripping nozzle separately, 63.5g (0.25mol) 37%SA, 66.7g (2.0g/mol, be reduced to respect to amount of monomer adding) 15%NaPS, and 78.6g (5.5g/mol is reduced to respect to amount of monomer adding) 35%SBS.Dropwise the time of Jia Ruing is 80%AA, and 37%SA and 35%SBS respectively did for oneself 300 minutes, and 15%NaPS is 310 minutes.But, SBS for 35%, it begins dropwise to add altogether in back 10 minutes 7.1g (0.5g/mol is reduced to respect to amount of monomer adding) in polymerization, in thereafter 290 minutes, add 71.5g (5.0g/mol is reduced to respect to amount of monomer adding) altogether.Polymerization temperature raises in polyreaction speed with 0.5 ℃ of per minute after 30 ℃ of initiations, and is constant at 90 ℃ after 120 minutes after the polymerization initiation beginning.
After dropwise add stopping, reaction soln kept 30 minutes so that ageing of solution and finish polymerization at 90 ℃.After polymerization was finished, reaction soln was cooled and neutralizes by stirring down to wherein dropwise adding 366.7g (4.40mol) 48%NaOH lentamente.Thus, obtaining solids concn is that 45 weight % and final degree of neutralization are the aqueous solution that contains sodium polyacrylate (below be referred to as " polymkeric substance (21) ") of 93mol%.Polymerizing condition brief summary used herein is in following table 4.
Resulting polymers (21) is measured its molecular weight thus, S value, R value, Q value, iron concentration, calcium-binding capacity, precipitation capacity under gas volume and the low temperature.The results are shown in table 11.
Embodiment 22
2.5 liters of the volumes of making at SUS have been installed in the separable flask of reflux exchanger and agitator and have been placed 156.5g pure water (first batch of reinforced) and be heated to 90 ℃ under whipped state.In being constant at about 90 ℃ gained polymerization reaction system, continuing under the stirring, dropwise add 427.5g (4.75mol) 80%AA by independently dripping nozzle separately, 63.5g (0.25mol) 37%SA, 66.7g (2.0g/mol, be reduced to respect to amount of monomer adding) 15%NaPS, and 71.4g (5.0g/mol is reduced to respect to amount of monomer adding) 35%SBS.Dropwise the time of Jia Ruing is 80%AA, and 37%SA and 35%SBS respectively did for oneself 240 minutes, and 15%NaPS is 250 minutes.
After dropwise adding termination, reaction soln keeps 30 minutes to finish polymerization at 90 ℃.After polymerization is finished, feed nitrogen with 1 liter/minute speed in reaction soln, aeration time is 30 minutes, to discharge sulfurous gas from reaction soln.Then, reaction soln is cooled.The aqueous solution that contains sodium polyacrylate that to obtain solids concn thus and be 53 weight % and final degree of neutralization be 5mol% (below be referred to as " polymkeric substance (22) ").Polymerizing condition brief summary used herein is in following table 5.
Resulting polymers (22) is measured its molecular weight thus, S value, R value, Q value, iron concentration, calcium-binding capacity, precipitation capacity under gas volume and the low temperature.The results are shown in table 11.
Embodiment 23
2.5 liters of the volumes of making at SUS have been installed in the separable flask of reflux exchanger and agitator and have been placed 156.5g pure water (first batch of reinforced) and be heated to 90 ℃ under whipped state.In being constant at about 90 ℃ gained polymerization reaction system, continuing under the stirring, dropwise add 427.5g (4.75mol) 80%AA by independently dripping nozzle separately, 63.5g (0.25mol) 37%SA, 66.7g (2.0g/mol, be reduced to respect to amount of monomer adding) 15%NaPS, and 71.4g (5.0g/mol is reduced to respect to amount of monomer adding) 35%SBS.Dropwise the time of Jia Ruing is 80%AA, and 37%SA and 35%SBS respectively did for oneself 240 minutes, and 15%NaPS is 250 minutes.
After dropwise adding termination, reaction soln keeps 30 minutes to finish polymerization at 90 ℃.After polymerization was finished, reaction soln was cooled and measures its content of sulfur dioxide, found that it is 1.2 grams.For reducing content of sulfur dioxide, the aqueous hydrogen peroxide solution that adds 1.1g (for the sulfurous gas equimolar amount) 35% in reaction soln (is designated hereinafter simply as " 35%H 2O 2").The aqueous solution that contains sodium polyacrylate that to obtain solids concn thus and be 53 weight % and final degree of neutralization be 5mol% (below be referred to as " polymkeric substance (23) ").Polymerizing condition brief summary used herein is in following table 5.
Resulting polymers (23) is measured its molecular weight thus, S value, R value, Q value, iron concentration, calcium-binding capacity, precipitation capacity under gas volume and the low temperature.The results are shown in table 11.
Embodiment 24
2.5 liters of the volumes of making at SUS have been installed in the separable flask of reflux exchanger and agitator and have been placed 156.5g pure water (first batch of reinforced) and be heated to 90 ℃ under whipped state.In being constant at about 90 ℃ gained polymerization reaction system, continuing under the stirring, dropwise add 427.5g (4.75mol) 80%AA by independently dripping nozzle separately, 63.5g (0.25mol) 37%SA, 66.7g (2.0g/mol, be reduced to respect to amount of monomer adding) 15%NaPS, and 71.4g (5.0g/mol is reduced to respect to amount of monomer adding) 35%SBS.Dropwise the time of Jia Ruing is 80%AA, and 37%SA and 35%SBS respectively did for oneself 240 minutes, and 15%NaPS is 250 minutes.
After dropwise adding termination, reaction soln keeps 30 minutes to finish polymerization at 90 ℃.After polymerization was finished, reaction soln was cooled then under continuing to stir by slowly dropwise to neutralize to the NaOH that wherein adds 366.7g (4.40mol) 48%.When measuring the content of sulfur dioxide of reaction soln, find that it is 1.8 grams.For reducing content of sulfur dioxide, in reaction soln, add the aqueous hydrogen peroxide solution of 1.7g (for the sulfurous gas equimolar amount) 35%.The aqueous solution that contains sodium polyacrylate that to obtain solids concn thus and be 45 weight % and final degree of neutralization be 93mol% (below be referred to as " polymkeric substance (24) ").Polymerizing condition brief summary used herein is in following table 5.
Resulting polymers (24) is measured its molecular weight thus, S value, R value, Q value, iron concentration, calcium-binding capacity, precipitation capacity under gas volume and the low temperature.The results are shown in table 11.
Table 4
Figure C20061009565300671
*: polyreaction is after 30 ℃ of initiations, and temperature raise with the speed of 1 ℃ of per minute and be constant at 90 ℃ after 60 minutes.
*: the add-on of 35%SBS in the time of 0-10 minute is 0.5g/mol, adds residual content in the time of 10-300 minute.
* *: polyreaction is after 30 ℃ of initiations, and temperature raise with the speed of 1 ℃ of per minute and be constant at 90 ℃ after 60 minutes.
* * *: polyreaction is after 30 ℃ of initiations, and temperature raise with the speed of 0.5 ℃ of per minute and be constant at 90 ℃ after 120 minutes.
Table 5
Figure C20061009565300691
Embodiment 25
2.5 liters of the volumes of making at SUS316, installed and placed the 185g pure water in the separable flask of reflux exchanger and agitator, 116g (1mol) maleic anhydride (being designated hereinafter simply as " MA acid anhydride "), 16.7g (0.2mol) 48% aqueous sodium hydroxide solution (being designated hereinafter simply as " 48%NaOH "), and under agitation be heated to 90 ℃.Then, by independently dripping a mouthful acrylic acid aqueous solution (being designated hereinafter simply as " 80%AA ") that in flask, dropwise adds 360g (4mol) 80% in the mixture under the stirring separately, 33.3g (0.4mol) 48%NaOH, 133.3g (4g/mol, be reduced to respect to amount of monomer adding) 15% sodium persulfate aqueous solution (being designated hereinafter simply as " 15%NaPS "), and 114.3g (8g/mol is reduced to respect to amount of monomer adding) the 35% Sodium Metabisulphate 65 aqueous solution (being designated hereinafter simply as " 35%SBS ").Dropwise the time of Jia Ruing is: 80%AA is 180 minutes, and 48%NaOH is 185 minutes, and 15%NaPS is 185 minutes, and 35%SBS is 175 minutes.All components dropwise add the time of beginning to be fixed.During this time, temperature remains on 90 ℃.This temperature dropwise adds at 80%AA and further kept 30 minutes after finishing so that ageing of solution and finish polymerization.After polymerization was finished, reaction soln was cooled and by to the NaOH neutralization that wherein adds 375g (4.5mol) 48%.Thus, obtain solids concn be 45 weight % and final degree of neutralization be 85mol% contain vinylformic acid/maleic acid (25).Polymerizing condition and molecular weight brief summary are in table 6.
Embodiment 26
Obtain vinylformic acid/maleic acid (26) by embodiment 25 steps, wherein the polymerizing condition of Gai Bianing is shown in table 6.Polymerizing condition and molecular weight brief summary are in table 6.
Embodiment 27
2.5 liters of the volumes of making at SUS316 have been installed in the separable flask of reflux exchanger and agitator and have been placed the 222g pure water, are heated to 90 ℃ under stirring.Then, in flask, dropwise add 116g (1mol) fusion MA acid anhydride in the water under the stirring by independently dripping mouth separately, 360g (4mol) 80%AA, 50g (0.6mol) 48%NaOH, 133.3g (4g/mol, be reduced to respect to amount of monomer adding) 15%NaPS, and 114.3g (8g/mol is reduced to respect to amount of monomer adding) 35%SBS.Dropwise the time of Jia Ruing is: the MA acid anhydride is 180 minutes, and 80%AA is 300 minutes, and 48%NaOH is 300 minutes, and 15%NaPS is 310 minutes, and 35%SBS is 290 minutes.All components dropwise add the time of beginning to be fixed.During this time, temperature remains on 90 ℃.This temperature dropwise adds at 80%AA and further kept 30 minutes after finishing so that ageing of solution and finish polymerization.After polymerization was finished, reaction soln was cooled and by to the NaOH neutralization that wherein adds 375g (4.5mol) 48%.Thus, obtaining solids concn is that 45 weight % and final degree of neutralization are vinylformic acid/maleic acid (27) of 85mol%.Polymerizing condition and molecular weight brief summary are in table 6.
Embodiment 28
2.5 liters of the volumes of making at SUS316 have been installed in the separable flask of reflux exchanger and agitator and have been placed the 208g pure water, are heated to 90 ℃ under stirring.Then, in flask, dropwise add 139g (1.5mol) methacrylic acid (be designated hereinafter simply as " MAA ") in the water under the stirring by independently dripping mouth separately, 315g (3.5mol) 80%AA, 20.8g (0.25mol) 48%NaOH, 100g (3g/mol, be reduced to respect to amount of monomer adding) 15%NaPS, and 85.7g (6g/mol is reduced to respect to amount of monomer adding) 35%SBS.Dropwise the time of Jia Ruing is: MAA is 180 minutes, and 80%AA is 180 minutes, and 48%NaOH is 180 minutes, and 15%NaPS is 185 minutes, and 35%SBS is 175 minutes.All components dropwise add the time of beginning to be fixed.During this time, temperature remains on 90 ℃.This temperature dropwise adds at 80%AA and further kept 30 minutes after finishing so that ageing of solution and finish polymerization.After polymerization was finished, reaction soln was cooled and by to the NaOH neutralization that wherein adds 375g (4.5mol) 48%.Thus, obtaining solids concn is that 45 weight % and final degree of neutralization are vinylformic acid/Sipacril 2739OF (28) of 95mol%.Polymerizing condition and molecular weight brief summary are in table 7.
Embodiment 29
2.5 liters of the volumes of making at SUS316 have been installed in the separable flask of reflux exchanger and agitator and have been placed the 114g pure water, are heated to 90 ℃ under stirring.Then, dropwise add 20.8g (0.2mol) vinylbenzene (being designated hereinafter simply as " St ") in the mixture under in flask, stirring, 342g (3.8mol) 80%AA, 15.8g (0.19mol) 48%NaOH, (106.7g 4g/mol is reduced to respect to amount of monomer adding) 15%NaPS, 91.4g (8g/mol, be reduced to respect to amount of monomer adding) 35%SBS, and the 5.2g pure water.Pure water mixes adding with 80%AA, other components dropwise add by independently dripping mouth separately simultaneously.Dropwise the time of Jia Ruing is: St is 150 minutes, and 80%AA is 180 minutes, and 48%NaOH is 180 minutes, and 15%NaPS is 190 minutes, and 35%SBS is 180 minutes.All components dropwise add the time of beginning to be fixed.During this time, temperature remains on 90 ℃.This temperature dropwise adds at 80%AA and further kept 30 minutes after finishing so that ageing of solution and finish polymerization.After polymerization was finished, reaction soln was cooled and by to the NaOH neutralization that wherein adds 285g (3.42mol) 48%.Thus, obtaining solids concn is that 45 weight % and final degree of neutralization are vinylformic acid/styrol copolymer (29) of 95mol%.Polymerizing condition and molecular weight brief summary are in table 8.
Embodiment 30
2.5 liters of the volumes of making at SUS316 have been installed in the separable flask of reflux exchanger and agitator and have been placed the 145g pure water, are heated to 90 ℃ under stirring.Then, dropwise add 43g (0.5mol) methyl acrylate (being designated hereinafter simply as " AM ") in the water under in flask, stirring, 405g (4.5mol) 80%AA, 18.8g (0.23mol) 48%NaOH, (133.3g 4g/mol is reduced to respect to amount of monomer adding) 15%NaPS, 114.3g (8g/mol, be reduced to respect to amount of monomer adding) 35%SBS, and the 10.8g pure water.Pure water mixes with 80%AA and is added dropwise to, and other components dropwise add by independently dripping mouth separately simultaneously.Dropwise the time of Jia Ruing is: AM is 180 minutes, and 80%AA and pure water are 180 minutes, and 48%NaOH is 180 minutes, and 15%NaPS is 185 minutes, and 35%SBS is 175 minutes.All components dropwise add the time of beginning to be fixed.During this time, temperature remains on 90 ℃.This temperature dropwise adds at 80%AA and further kept 30 minutes after finishing so that ageing of solution and finish polymerization.After polymerization was finished, reaction soln was cooled and by to the NaOH neutralization that wherein adds 337.5g (4.05mol) 48%.Thus, obtaining solids concn is that 45 weight % and final degree of neutralization are vinylformic acid/methyl acrylate copolymer (30) of 95mol%.Polymerizing condition and molecular weight brief summary are in table 9.
Table 6
Figure C20061009565300731
Table 7
Figure C20061009565300741
Table 8
Table 9
Figure C20061009565300761
Comparative Examples 1
5 liters of the volumes of making at SUS have been installed in the separable flask of reflux exchanger and agitator and have been placed 350g pure water (first batch of reinforced) and be heated to boiling point under whipped state.Then, in the polymerization reaction system that under boiling point, is in reflux state and continues to stir, dropwise add 900g (10mol) 80%AA by independently dripping nozzle separately, 266.7g (4.0g/mol, be reduced to respect to amount of monomer adding) 15%NaPS, (228.6g 8.0g/mol is reduced to respect to amount of monomer adding) 35%SBS, and 83.3g (1mol) 48%NaOH.Dropwise the time of Jia Ruing is: 80%AA and 48%NaOH are 180 minutes, and 15%NaPS and 35%SBS are 190 minutes.Each component is dropwise dropwise adding with fixed speed respectively in the joining day accordingly continuously.
After dropwise add stopping, reaction soln kept 30 minutes so that ageing of solution and finish polymerization at boiling point.After polymerization was finished, reaction soln was cooled and neutralizes by stirring down to the NaOH that wherein dropwise adds 225g (2.7mol) 48% lentamente.Thus, obtaining solids concn is that 45 weight % and final degree of neutralization are the aqueous solution that contains sodium polyacrylate (below be referred to as " comparative polymer (1) ") of 37mol%.Polymerizing condition brief summary used herein is in following table 10.
Gained comparative polymer (1) is measured its molecular weight thus, S value, R value, Q value, iron concentration, calcium-binding capacity, precipitation capacity under gas volume and the low temperature.The results are shown in table 11.
Comparative Examples 2
5 liters of the volumes of making at SUS have been installed in the separable flask of reflux exchanger and agitator and have been placed 150g pure water (first batch of reinforced) and be heated to boiling point under whipped state.Then, in the polymerization reaction system that under boiling point, is in reflux state and continues to stir, by independently dripping nozzle separately, dropwise add 900g (10mol) 80%AA in equally during 120 minutes, (266.7g 4.0g/mol is reduced to respect to amount of monomer adding) 15%NaPS, 228.6g (8.0g/mol, be reduced to respect to amount of monomer adding) 35%SBS, and the 11.4g pure water.Each component is dropwise dropwise adding with fixed speed respectively in the joining day accordingly continuously.
After dropwise add stopping, reaction soln kept 30 minutes so that ageing of solution and finish polymerization at boiling point.After polymerization was finished, reaction soln was cooled and neutralizes by stirring down to the NaOH that wherein dropwise adds 750g (9.0mol) 48% lentamente.Thus, obtaining solids concn is that 45 weight % and final degree of neutralization are the aqueous solution that contains sodium polyacrylate (below be referred to as " comparative polymer (2) ") of 90mol%.Polymerizing condition brief summary used herein is in following table 10.
Gained comparative polymer (2) is measured its molecular weight thus, S value, R value, Q value, iron concentration, calcium-binding capacity, precipitation capacity under gas volume and the low temperature.The results are shown in table 11.
Comparative Examples 3
2.5 liters of the volumes of making at SUS have been installed in the separable flask of reflux exchanger and agitator and have been placed 133.5g pure water (first batch of reinforced) and be heated to boiling point under whipped state.Then, in the polymerization reaction system that under boiling point, is in reflux state and continues to stir, dropwise add 405.0g (4.50mol) 80%AA by independently dripping nozzle separately, 127.0g (0.50mol) 37%SA, 66.7g (2.0g/mol, be reduced to respect to amount of monomer adding) 15%NaPS, and 85.7g (6.0g/mol is reduced to respect to amount of monomer adding) 35%SBS.Dropwise the joining day is: 80%AA, and 37%SA, and 35%SBS is 240 minutes and 15%NaPS is 250 minutes.
After dropwise add stopping, reaction soln kept 30 minutes so that ageing of solution and finish polymerization at boiling point.After polymerization was finished, reaction soln was cooled and neutralizes by stirring down to the NaOH that wherein dropwise adds 345.8g (415mol) 48% lentamente.Thus, obtaining solids concn is that 45 weight % and final degree of neutralization are the aqueous solution that contains sodium polyacrylate (below be referred to as " comparative polymer (3) ") of 93mol%.Polymerizing condition brief summary used herein is in following table 10.
Gained comparative polymer (3) is measured its molecular weight thus, S value, R value, Q value, iron concentration, calcium-binding capacity, precipitation capacity under gas volume and the low temperature.The results are shown in table 11.
Comparative Examples 4
2.5 liters of the volumes of making at SUS have been installed in the separable flask of reflux exchanger and agitator and have been placed 635.3g pure water (first batch of reinforced) and be heated to boiling point under whipped state.Then, in the polymerization reaction system that under boiling point, is in reflux state and continues to stir, dropwise add 762.5g (3.0mol) 37%SA, 24.0g (1.2g/mol by independently dripping nozzle separately, be reduced to respect to amount of monomer adding) 15%NaPS, and the 82.3g pure water.Dropwise the joining day is: 37%SA is 200 minutes and 15%NaPS and pure water are 205 minutes.
After dropwise add stopping, reaction soln kept 30 minutes so that ageing of solution and finish polymerization at boiling point.After polymerization was finished, reaction soln was cooled.Thus, obtaining solids concn is that 20 weight % and final degree of neutralization are the aqueous solution that contains sodium polyacrylate (below be referred to as " comparative polymer (4) ") of 100mol%.Polymerizing condition brief summary used herein is in following table 10.
Gained comparative polymer (4) is measured its molecular weight thus, S value, R value, Q value, iron concentration, calcium-binding capacity, precipitation capacity under gas volume and the low temperature.The results are shown in table 11.
Table 10
Calcium-binding ability trends towards improving with the molecular weight increase in the table 11.Therefore this result must be between the sample with approximately identical molecular weight relatively.For result shown in the table 11, polymkeric substance (20) is the sample with roughly the same molecular weight with comparative polymer (1), and calcium-binding capacity is 252 to polymkeric substance (20), and comparative polymer (1) is 231, that is, polymkeric substance (20) obviously is better than comparative polymer (1).It should be noted that polymkeric substance (16), for example, have very little molecular weight although it is compared with comparative polymer (1), its calcium-binding capacity is higher.
Incidental, this polymkeric substance is compared the Q value (being the antigelation ability) with big representative antigelation ability with comparative polymer (1) with (2).This fact can be by following hypothesis pragmatize.
The antigelation ability is considered the characteristic of its evaluation method, trends towards reducing with the increase of polymer concentration.Polymkeric substance in the embodiment of the invention has successfully significantly reduced foreign matter content, therefore, show the comparative polymer (1) that has high impurity content and (2) worse antigelation ability inevitably (for this point, referring to precipitation capacity under the low temperature, the S value, the calcium-binding capacity data).Therefore, the data of being discussed show that not necessarily polymkeric substance of the present invention is poorer on the antigelation ability.
[for unsaturated alkylene glycol copolymer]
Unsaturated alkylene glycol copolymer that the present invention produces, measure or detect the amount of contained S in its (2-1) given polymkeric substance and the total amount and the dialysis process that is used for it is measured of S by following method, (2-2) weight-average molecular weight (Mw) and number-average molecular weight (Mn), (2-3) be used to measure the degree of gelation of antigelation ability, (2-4) tone (b value), (2-5) calcium-binding capacity, (2-6) clay dispersion ability and (2-7) and the consistency of liquid washing agent.
For these projects, (2-1) reach (2-3) according to the process evaluation among the embodiment of above-mentioned production (methyl) acrylic acid polymer.That is, they respectively with (1-1) and (1-3) identical, except substituting (methyl) acrylic acid polymer with unsaturated alkylene glycol copolymer.
(2) mensuration of weight-average molecular weight (Mw) and number-average molecular weight (Mn)
Weight-average molecular weight of given unsaturated alkylene glycol copolymer (Mw) and number-average molecular weight (Mn) are measured by GPC (gel permeation chromatography).It is as described below to measure used analysis condition and instrument.
Instrument: Hitachi, Ltd. produce with product code name " L-7000series " product sold.
Detector: RI
Post: Shodex Corp. produce with product code name " SB-G ", " SB-804 ", " SB-803 ", " SB-802.5 " product sold.
Column temperature: 40 ℃
Working curve: Sowa Kagaku K.K. produce with registered trademark Polyacrylic Acid Standard product sold.
GPC software: Nippon Bunko K.K. produce with registered trademark " BORWIN " product sold
Eluant: 0.1M phosphoric acid buffer (PH8.0)/acetonitrile=9/1 (weight ratio)
(4) tone (b value)
Given polymkeric substance or aqueous solutions of polymers dilute or be concentrated into polymer concentration is 40 weight %.Test the transmitance of the prepared aqueous solution to measure laboratory-scale b value by the colorimeter that uses Nippon Denshoku Kogyo K.K. to produce with product code " ND-1001DP " sale.The b value is that the quantity of corresponding b value is increasing on direction when the yellow chromaticity of the given aqueous solution strengthens.
(5) measurement of calcium-binding capacity
For the calcium ion standardized solution that is used for working curve, to prepare concentration respectively be the 0.01mol/ liter with 50 gram Calcium dichloride dihydrates of fixed amount, 0.001mol/ liter, the aqueous solution that 0.0001mol/ rises.NaOH solution with 4.8% adds the together thorough sample solution that is used for working curve with preparation that stirs of Klorvess Liquid (being designated hereinafter simply as " the 4M-KCl aqueous solution ") that 4mol/ wherein rises with magnetic stirring apparatus with itself and 1ml with its pH regulator to the scope of 9-11 and further.For the calcium ion standardized solution that is used to test, prepare the Calcium dichloride dihydrate solution (every duplicate samples 50 grams) that 0.001mol/ rises with aequum.
Then, in a 100ml beaker, putting into to be reduced to solid constituent content is that the amount of 10mg weighs up a specimen (polymkeric substance) and together thoroughly stirs with magnetic stirring apparatus with the above-mentioned calcium ion standardized solution to be measured of 50g then.In addition, similar to the working curve sample, the NaOH solution with 4.8% is made specimen solution with its pH regulator to the scope of 9-11 and by the 4M-KCl aqueous solution that adds 1ml.
Working curve sample solution that makes like this and specimen solution are analyzed with calcium ion electrode 93-20 and reference electrode 90-01, the two is made by Orion K.K., analyzes in the titration apparatus that Hiranuma Sangyo K.K. makes and sells with registered trademark " COMTITE-550 " and carries out.
Given sample (polymkeric substance) institute bonded calcium ion amount is used for the value that the sample of working curve and test measures by utilization and calculates.This amount, the amount of the corresponding polymer solids material of promptly every gram institute bonded calcium ion is represented with the quantitative value of the mg that is reduced to lime carbonate.This amount is reported as the value of calcium-binding capacity.
(6) clay dispersion ability
By with pure water with the 67.56g glycine, 52.6g sodium-chlor and 2.4 gram NaOH release to 600g and make damping fluid.Adding 60 (60) g damping fluids and 0.3268g Calcium dichloride dihydrate simultaneously and further being diluted to gross weight with pure water then is 1000g (as damping fluid).The given aqueous copolymers solution of four (4) g (being reduced to the amount of solid constituent), 0.1 weight % and 36g adding damping fluid wherein together are stirred to and obtain dispersion.In the testing tube (making) of the high 180mm of a diameter 18mm by Iwaki Glass K.K., adding 0.3g clay (Nippon Funtai Kogyo Gijutsu Kyokai Corp. produces and sells with product code name " TestingDust Type 8 ") also to wherein adding the above-mentioned dispersion of 30g, together is encapsulated in them in the testing tube.
Testing tube vibrates to clay and is disperseed equably.Thereafter, testing tube left standstill 20 hours at the dark place.After leaving standstill in 20 hours, the 5ml material of getting dispersion surface is tested its specific absorption also with the sample pool of 1cm with UV spectrum (Shimadzu Seisakusho K.K. produces and sells with product code name " UV-1200 ") under the 380nm wavelength.Specific absorption is big more, and the clay dispersion ability is strong more.
(7) with the consistency of liquid washing agent
The detergent use that contains the following example gained new copolymer is in the consistency of test itself and liquid washing agent.
Prepare different washing composition with embodiment gained new copolymer and following component.These materials thoroughly are stirred to each component to be mixed equably, and the gained sample is at 25 ℃ of its turbidity of test.The turbidometer that Nippon Denshoku K.K. produces and sells with product code name " NDH2000 " is used to turbidimetry (kaolin turbidity mg/ liter).
The result carries out classification according to following 3 scales, wherein
Zero: turbidity value (0-50 (mg/ liter)), no vision can debate not Fen Li, precipitation, or muddy sign
△: turbidity value (50-200 (mg/ liter)) has vision can debate other slight muddy sign
*: turbidity value (being not less than 200 (mg/ liters)) vision occurs and can debate other muddy sign
Detergent formulation:
SFT-70H (Ltd. produces for Softanol 70H Voranol EP 2001, Nippon Shokubai Co.): 11g
Neopelex F-65 (Sodium dodecylbenzene sulfonate that Kao Corportation produces): 32g
Diethanolamine: 10g
Ethanol: 5g
Propylene glycol: 15g
Embodiment gained new copolymer and comparative polymer: 1.5g (separately)
Water: surplus
Embodiment 31
2.5 liters of the volumes of making at SUS have been installed in the separable flask of reflux exchanger and agitator and have been placed 145.0g pure water (first batch of reinforced) and be heated to 90 ℃ under whipped state.
Then, under being constant at about 90 ℃ of temperature and in the polymerization reaction system that continues to stir, dropwise add the acrylic acid aqueous solution (being designated hereinafter simply as " 80%AA ") of 180.0g (2.00mol) 80% by independently dripping nozzle separately, 8.33g (0.10mol) 48% sodium hydroxide (being designated hereinafter simply as " 48%NaOH "), 328.8g (0.50mol) unsaturated alcohol, it derives from the 3-methyl-3-butene-1-alcohol (being designated hereinafter simply as " 80%IPN-10 ") with 10mol oxyethane adding 80%, 66.7g (4.0mol, be reduced to respect to adding amount of monomer (wherein, term " add amount of monomer " refers to all add monomeric total amounts; Hereinafter its implication is similar)) 15% sodium persulfate aqueous solution (being designated hereinafter simply as " 15%NaPS "), 57.1g (8.0g/mol, be reduced to respect to amount of monomer adding) the 35% Sodium Metabisulphate 65 aqueous solution (being designated hereinafter simply as " 35%SBS ") and 100g pure water.Dropwise the time of Jia Ruing is that 80%AA and 48%NaOH are 180 minutes, and 80%IPN-10 is 170 minutes, and 35%SBS is 175 minutes, and 15%NaPS and pure water are 210 minutes.In whole dropwise adition process, relevant component adds continuously with the fixed drop rate.
After dropwise add stopping, reaction soln kept 30 minutes so that ageing of solution and finish polymerization at 90 ℃.After polymerization was finished, reaction soln was cooled and neutralizes by stirring down to the aqueous sodium hydroxide solution that wherein dropwise adds 75.0g (0.90mol) 48% lentamente.Thus, obtaining solids concn is that 45 weight % and final degree of neutralization are the unsaturated alkylene glycol copolymer (below be referred to as " polymkeric substance (31) ") of 50mol%.Polymerizing condition brief summary used herein is in following table 12.
Resulting polymers (31) is measured its molecular weight thus, the S value, the b value, q value or Q value, calcium-binding capacity, the clay dispersion ability and with the consistency of liquid washing agent.The results are shown in down tabulation 18 and 20.
Embodiment 32-39
Obtain polymkeric substance (32)-(39) by embodiment 31 steps.The brief summary of polymkeric substance condition is in following table 12 and 13.
Its molecular weight is measured in resulting polymers (32)-(39) thus, the S value, the b value, q value or Q value, calcium-binding capacity, the clay dispersion ability and with the consistency of liquid washing agent.The results are shown in down tabulation 18 and 20.
Table 12
Table 13
Figure C20061009565300861
Embodiment 40-42
Obtain polymkeric substance (40)-(42) by embodiment 31 steps, wherein substitute 80%IPN-10 with the 3-methyl-3-butene-1-pure gained unsaturated alcohol (being designated hereinafter simply as " 50%IPN-50 ") that derives from 50mol oxyethane adding 50%.The brief summary of polymkeric substance condition is in following table 14.
Its molecular weight is measured in resulting polymers (40)-(42) thus, the S value, the b value, q value or Q value, calcium-binding capacity, the clay dispersion ability and with the consistency of liquid washing agent.The results are shown in down tabulation 18 and 20.
Table 14
Figure C20061009565300881
Embodiment 43
Obtain this polymkeric substance by embodiment 31 steps, wherein substitute 80%IPN-10 with the vinyl carbinol gained unsaturated alcohol (being designated hereinafter simply as " 80%PEAA-5 ") that derives from 5mol oxyethane adding 80%.The brief summary of polymkeric substance condition is in following table 15.
Resulting polymers (43) is measured its molecular weight thus, the S value, the b value, q value or Q value, calcium-binding capacity, the clay dispersion ability and with the consistency of liquid washing agent.The results are shown in down tabulation 18 and 20.
Table 15
Embodiment 44
Obtain polymkeric substance (44) by embodiment 31 steps, wherein use maleic anhydride (being designated hereinafter simply as " 100%MA ") as the 3rd monomer component.The brief summary of polymkeric substance condition is in following table 16.
Resulting polymers (44) is measured its molecular weight thus, the S value, the b value, q value or Q value, calcium-binding capacity, the clay dispersion ability and with the consistency of liquid washing agent.The results are shown in down tabulation 18 and 20.
Table 16
Figure C20061009565300921
Embodiment 45
Obtain polymkeric substance (45) by embodiment 31 steps, wherein use 100% methacrylic acid (being designated hereinafter simply as " 100%MAA ") as the 3rd monomer component.The brief summary of polymkeric substance condition is in following table 17.
Resulting polymers (45) is measured its molecular weight thus, the S value, the b value, q value or Q value, calcium-binding capacity, the clay dispersion ability and with the consistency of liquid washing agent.The results are shown in down tabulation 18 and 20.
Table 17
Figure C20061009565300941
Comparative Examples 5
At volume is 1000ml, and agitator has been installed, condenser, thermometer, the IPN-10 aqueous solution of placement 200g 63.87 weight % in the separable flask of a nitrogen input tube and an addition funnel, under the condition that atmosphere is replaced by nitrogen in flask, the aqueous solution is heated to 65 ℃ under whipped state.When temperature reached prescribed value, disposable aqueous hydrogen peroxide solution with 1.58g 30 weight % all added.Then, dropwise add the vinylformic acid of 32.61g 100 weight % respectively in the solution in flask, the thiohydracrylic acid aqueous solution of the L-aqueous ascorbic acid of 29.29g 2.1 weight % and 17.22g 3 weight %.Acrylic Acid Monomer and thiohydracrylic acid dropwise added and the dropwise adding in 90 minutes of L-xitix in 60 minutes.After the L-aqueous ascorbic acid dropwise adds termination, the gained reaction soln under same temperature ageing 120 minutes to finish polymerization and to obtain comparative polymer (5).
Gained comparative polymer (5) is measured its molecular weight thus, the S value, the b value, the Q value, calcium-binding capacity, the clay dispersion ability and with the consistency of liquid washing agent.The results are shown in down tabulation 18 and 19.
Comparative Examples 6
At volume is 500ml, and agitator has been installed, condenser, and thermometer is placed the 167.24g pure water in the separable flask of a nitrogen input tube and an addition funnel, and under the condition that atmosphere is replaced by nitrogen in flask, water is heated to 95 ℃ under whipped state.The ammonium persulfate aqueous solution that dropwise adds 28.9g 3 weight % respectively in the solution in flask, the IPN-25 aqueous solution of 82.67g 50 weight % and by with 8.25g 80% acrylic acid aqueous solution and 48.75g 40% ammonium acrylate mixing obtained aqueous solution.IPN-25 and Acrylic Acid Monomer dropwise added and ammonium persulfate aqueous solution dropwise adding in 150 minutes in 120 minutes.After IPN-25 and Acrylic Acid Monomer dropwise add termination, the gained reaction soln under same temperature ageing 30 minutes to finish polymerization.After the polymerization, reaction soln forms comparative polymer (6) by the ammonia soln that adds 1.5g 28%.
Gained comparative polymer (6) is measured its molecular weight thus, the S value, the b value, the Q value, calcium-binding capacity, the clay dispersion ability and with the consistency of liquid washing agent.The results are shown in down tabulation 18 and 19.
Comparative Examples 7
At volume is 500ml, and agitator has been installed, condenser, and thermometer is placed the 174.2g pure water in the separable flask of a nitrogen input tube and an addition funnel, and under the condition that atmosphere is replaced by nitrogen in flask, water is heated to 100 ℃ under whipped state.When temperature reaches prescribed value, the sodium persulfate aqueous solution that dropwise adds 32.5g 3 weight % respectively in the solution in flask, 82.67g the IPN-10 aqueous solution of 50 weight % and by with 8.25g 80% acrylic acid aqueous solution and 56.2g 37% sodium acrylate mixing obtained aqueous solution.IPN-10 and Acrylic Acid Monomer dropwise added and sodium persulfate aqueous solution dropwise adding in 150 minutes in 120 minutes.After IPN-10 and Acrylic Acid Monomer dropwise add termination, the gained reaction soln under same temperature ageing 30 minutes to finish polymerization.After the polymerization, reaction soln forms comparative polymer (7) by the sodium hydroxide that adds 7.43g 48%.
Gained comparative polymer (7) is measured its molecular weight thus, the S value, the b value, the Q value, calcium-binding capacity, the clay dispersion ability and with the consistency of liquid washing agent.The results are shown in down tabulation 18 and 19.
Comparative Examples 8
At volume is 1000ml, and agitator has been installed, condenser, and thermometer is placed the 312.9g pure water in the separable flask of a nitrogen input tube and an addition funnel, and under the condition that atmosphere is replaced by nitrogen in flask, water is heated to 100 ℃ under whipped state.When temperature reaches prescribed value, the sodium persulfate aqueous solution that dropwise adds 68.9g 10 weight % respectively in the solution in flask, 32.5g the IPN-10 aqueous solution of 80 weight % and by with 15.6g 80% acrylic acid aqueous solution and 332.1g 37% sodium acrylate mixing obtained aqueous solution.IPN-10 and Acrylic Acid Monomer dropwise added and sodium persulfate aqueous solution dropwise adding in 150 minutes in 120 minutes.After IPN-10 and Acrylic Acid Monomer dropwise add termination, the gained reaction soln under same temperature ageing 30 minutes to finish polymerization and to obtain comparative polymer (8).
Gained comparative polymer (8) is measured its molecular weight thus, the S value, the b value, the Q value, calcium-binding capacity, the clay dispersion ability and with the consistency of liquid washing agent.The results are shown in down tabulation 18 and 19.
Table 18
Polymkeric substance Monomer A/B/C (reinforced ratio, weight ratio) Monomer A Monomers B Monomer C Molecular weight, Mw
(31) 35/65/0 AA IPN-10 - 23000
(32) 80/20/0 AA IPN-10 - 6500
(33) 72/28/0 AA IPN-10 - 8400
(34) 72/28/0 AA IPN-10 - 14000
(35) 65/35/0 AA IPN-10 - 15000
(36) 50/50/0 AA IPN-10 - 15000
(37) 72/28/0 AA IPN-10 - 12000
(38) 65/35/0 AA IPN-10 - 9100
(39) 90/10/0 AA IPN-10 - 5300
(40) 80/20/0 AA IPN-50 - 5800
(41) 72/28/0 AA IPN-50 - 6500
(42) 90/10/0 AA IPN-50 - 7700
(43) 72/28/0 AA PEA-5 - 6500
(44) 60/35/5 AA IPN-10 MA 14000
(45) 60/20/20 AA IPN-10 MAA 7600
Table 19
Comparative polymer Monomer A/B/C (reinforced ratio, weight ratio) Monomer A Monomers B Monomer C Molecular weight, Mw
(5) 25/75/0 AA IPN-10 - 92000
(6) 35/65/0 AA IPN-25 - 17000
(7) 35/65/0 AA IPN-10 - 5900
(8) 80/20/0 AA IPN-10 - 6000
Table 20
Embodiment Polymkeric substance The S value B value (40%) Sequestering power Dispersive ability The q value The Q value Consistency
31 (31) 5 1 105 0.3 - 55 ○
32 (32) 9 ＜1 215 0.5 0.008 - ○
33 (33) 8 1 205 0.5 0.004 - ○
34 (34) 12 ＜1 215 0.4 0.002 - ○
35 (35) 13 ＜1 215 0.3 0.003 - ○
36 (36) 7 1 170 0.3 - 145 ○
37 (37) 11 ＜1 225 0.4 0.003 - ○
38 (38) 17 ＜1 200 0.4 0.005 - ○
39 (39) 16 ＜1 220 0.4 0.010 - ○
40 (40) 16 1 210 0.4 0.089 - ○
41 (41) 11 ＜1 200 0.4 0.078 - ○
42 (42) 20 ＜1 215 0.4 0.073 - ○
43 (43) 12 1 195 0.3 - 190 ○
44 (44) 18 1 235 0.3 0.005 - ○
45 (45) 16 1 210 0.4 0.002 - ○
Comparative Examples Comparative polymer
5 (5) 0 3 60 0.2 - 4 ○
6 (6) 0 11 90 0.3 - 20 ○
7 (7) 0 4 85 0.3 - 24 ○
8 (8) 0 8 195 0.4 - 15 ○
The present invention's (methyl) acrylic acid polymer, although its polymer phase that has the antigelation ability with tradition is than having relative bigger molecular weight, it not only shows high sequestering power and dispersing property but also has than the better antigelation performance of traditional polymer.Particularly introduce the requirement of the S amount of element sulphur amount, and satisfy above-mentioned R value by satisfying above-mentioned representative, the requirement of the Q value of iron concentration and above-mentioned representative antigelation ability, this polymkeric substance can significantly reduce foreign matter content.This polymkeric substance has high quality and has excellent in storage stability, the problem that it has been avoided in low tempertaure storage process degradation and has been settled out impurity.Therefore, it can be advantageously used in following purposes such as dispersion agent, washing agent, detergent builder.In addition, it compares aspect cost obviously excellent with traditional polymer.
The production method of (methyl) of the present invention acrylic acid polymer can be produced under the NO high density effectively in the past has low-molecular-weight polymkeric substance.By carrying out polyreaction at low temperatures in long-time, this method can suppress the discharging of sulfur dioxide gas.And by the consumption (preferred also by reducing the degree of neutralization in the polymerization process) that reduces initiator, this method can make the generation of impurity be suppressed.By this method, can produce (methyl) acrylic acid polymer with the performance that has significantly improved.(methyl) acrylic acid polymer that generates neither can make performance reduce in the low tempertaure storage process, also is not settled out impurity.In addition, it can be stablized and the high-performance that keeps in the production process consistently to be obtained and be not subjected to the influence (that is, it can show the performance that it obtained with being entirely satisfactory and not demoted) of storage environment.
Because this method can make in the polyreaction of initiator system under obviously being considered as making the low temperature of undercapacity and make us bringing into play very satisfactorily its function, it has avoided adding the necessity of excessive initiator in polymerization reaction system.Therefore, it can suppress the rising of cost in the polymerization production and enhance productivity, and can suppress the discharging and the contamination precipitation of oxidizing sulfur dioxide.
In addition, by the inventive method, it can obtain making the S value of representing the element sulphur amount of introducing, the R value, and iron concentration is represented the Q value of antigelation ability, and further weight-average molecular weight is in (methyl) acrylic acid polymer in the specialized range.This polymkeric substance shows most effectively as dispersiveness, the different properties of sequestering power and antigelation performance etc.This high-quality polymkeric substance can obtain in the high density polymerization process in a step, and need not increase the initiator of any amount.Therefore, this method is by saving the raising that enrichment step has greatly improved productivity and effectively suppressed production cost.
Washing composition of the present invention contains above-mentioned (methyl) acrylic acid polymer.Therefore, it has formed and has combined dispersiveness, the high performance detergent builder of sequestering power and antigelation ability.It neither can or not be settled out impurity because of time lengthening makes degradation yet in low tempertaure storage, and can stablize and the high-performance that keeps in the production process consistently to be obtained and be not subjected to the influence of storage environment.This product of the present invention can be made significant contribution to the raising of washing composition quality.
Unsaturated alkylene glycol copolymer has high sequestering power and compares the better antigelation performance of demonstration with dispersiveness and with traditional polymer.Particularly by satisfying the requirement of representing the S value of the element sulphur of introducing defined above, it can significantly suppress the generation of impurity.It is excellent and can avoid the degradation that causes because of low tempertaure storage and produce problem such as impurity that this polymkeric substance has high quality and package stability.Therefore, it can be advantageously used in following purposes such as dispersion agent, washing agent, detergent builder, and cement additire.In addition, it compares aspect cost obviously superior with traditional polymer.
The method of producing unsaturated alkylene glycol copolymer by the present invention, the high density that can traditional method never reaches is produced low-molecular-weight polymkeric substance effectively.In addition, by carrying out polymerization at low temperatures for a long time, it can suppress the generation of sulfur dioxide gas.By the consumption (preferred also by reducing the degree of neutralization in the polymerization process) that reduces initiator, this method can make the generation of impurity be suppressed.By this method, can produce unsaturated alkylene glycol copolymer with the performance that has significantly improved.The unsaturated alkylene glycol copolymer that generates performance is reduced, be not settled out impurity yet.In addition, its can stablize and keep consistently institute's inherent high-performance in the production process and be not subjected to the influence (that is, it can show the performance that it obtained with being entirely satisfactory and not demoted) of storage environment.
Because the inventive method can make in the polyreaction of initiator system under obviously being considered as making the low temperature of undercapacity and make us bringing into play very satisfactorily its function, it has avoided adding the necessity of excessive initiator in polymerization reaction system.Therefore, it can suppress the rising of cost in the polymerization production and enhance productivity, and can suppress the discharging and the contamination precipitation of sulfur dioxide gas.
In addition, by the inventive method, it can obtain making S value and the weight-average molecular weight of representing the element sulphur amount of introducing to be in the interior unsaturated alkylene glycol copolymer of specialized range.This polymkeric substance shows most effectively as dispersiveness, the different properties of sequestering power and antigelation performance etc.In addition, this high-quality polymkeric substance can obtain in the high density polymerization process in a step, and need not increase the consumption of initiator.Therefore, this method is by saving the raising that enrichment step has greatly improved productivity and effectively suppressed production cost.
Washing composition of the present invention contains above-mentioned unsaturated alkylene glycol copolymer.Therefore, it has formed and has combined dispersiveness, the high performance detergent builder of sequestering power and antigelation ability.It neither can or not be settled out impurity because of time lengthening makes degradation yet in low tempertaure storage, and can stablize and the high-performance that keeps in the production process consistently to be obtained and be not subjected to the influence of storage environment.Therefore, it can make significant contribution to the raising of washing composition quality.
The 2002-180455 that submits on Japanese patent application 2001-307757 that submit to October 3 calendar year 2001 and June 20 calendar year 2001 is all open, comprises specification sheets, claims, and accompanying drawing, and summary is incorporated herein by reference in full at this.

Claims (8)

1. unsaturated alkylene glycol copolymer, this multipolymer produces by (methyl) acrylic type monomer A and the copolymerization of unsaturated polyalkylene glycol type monomers B, wherein this multipolymer has rhodanine on its end group, and represent the S value of the element sulphur amount of introducing to be not less than 3, it defines by following formula, S=(contained quantity of S in the polymkeric substance)/(total quantity of S) * 100, and
The weight-average molecular weight Mw of this multipolymer is 2000-100,000, and
This multipolymer by containing 30-99 weight % (methyl) acrylic type monomer and unsaturated polyalkylene glycol type monomer combination polymerization in the aqueous solution of 1-70 weight % make;
Described rhodanine is acidic-group and the salt thereof that contains sulphur atom and Sauerstoffatom;
Described total quantity of S be the unsaturated alkylene glycol copolymer place mutually in the amount of contained whole S.
2. multipolymer as claimed in claim 1, wherein a kind of can with the monoethylenically unsaturated monomer C of monomer A and B copolymerization by copolymerization.
3. multipolymer as claimed in claim 1, the tone of the 40 weight % aqueous solution of this multipolymer, promptly the b value is not more than 2.
4. method of producing the unsaturated alkylene glycol copolymer of claim 1, it is characterized in that by with (methyl) acrylic type monomer A and the copolymerization of unsaturated polyalkylene glycol type monomers B, wherein the combination of one or more of persulphate and bisulfite is used as initiator, wherein based on the persulphate of a weight part, the amount of bisulfite is the 0.1-10 weight part, total weight range of described initiator is every mole of monomer 1-30 gram, polymerization temperature is 25-99 ℃, and the total duration that dropwise adds each component in the polymerization process is 180-600 minute.
5. method as claimed in claim 4, wherein a kind of can with the monoethylenically unsaturated monomer C of monomer A and B copolymerization by copolymerization.
6. detergent builder that contains multipolymer as claimed in claim 1.
7. liquid washing agent that contains multipolymer as claimed in claim 1.
8. washing composition that contains multipolymer as claimed in claim 1.
CNB2006100956538A 2001-10-03 2002-10-03 (methyl) acrylic acid polymer and unsaturated alkylene glycol copolymer and production method thereof Expired - Fee Related CN100564411C (en)

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