CN103214617A - Emulsion polymerization reaction method - Google Patents
Emulsion polymerization reaction method Download PDFInfo
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- CN103214617A CN103214617A CN2013101012213A CN201310101221A CN103214617A CN 103214617 A CN103214617 A CN 103214617A CN 2013101012213 A CN2013101012213 A CN 2013101012213A CN 201310101221 A CN201310101221 A CN 201310101221A CN 103214617 A CN103214617 A CN 103214617A
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Abstract
The invention discloses an emulsion polymerization reaction method comprising the steps that: 1, a core emulsion is prepared, wherein a 3/4 composite initiator solution is divided into four parts; a reaction temperature is maintained at 75 DEG C; a first part of the composite initiator solution is added into a reaction kettle and is mixed with a seed emulsion; rest 3/4 of a pre-emulsification liquid is dropped in within 1h, wherein a second part of the composite initiator solution is supplemented with a time interval of 30min; 2, a shell emulsion is prepared, wherein an emulsification agent in a sub-emulsification liquid is added into the reaction kettle in one time; a third part of the composite initiator is supplemented, and sub-emulsification liquid monomer is dropped in; after 30min, a fourth part of the composite initiator is dropped in, and the dropping is finished 20min before the dropping of the sub-emulsification liquid monomer; the temperature is increased to 80 DEG C, and a reaction is carried out for 2h; the temperature is reduced to room temperature, and a 10% adipic dihydrazide water solution is slowly added; the pH value is neutralized to 7-8 by using ammonia water; and filtering is carried out, such that waterborne polyacrylate emulsion is prepared. According to the invention, the preparation process and the product are cleaner, such that requirements of green, environment-friendly, and healthy are satisfied. The invention keeps pace with the trend.
Description
Technical field
The present invention relates to a kind of apparel binding fibre does not have the preparation method that the powder base is starched with the self-cross linking type water polyacrylic acid, relates in particular to the emulsion polymerization method of preparation water polyacrylic acid emulsion.
Background technology
Double-point lining cloth is since emerging, because its over-all properties is superior, outward appearance is beautiful, outstanding advantage such as wide application, in less than the development course in 10 years, become the topmost variety type of China's lining cloth industry, also opened new page for the modernized new coating technology that improves clothes grade and value added.But, technically, the special-purpose no powder base of two point is starched this piece field, so far also have randomness and blindness, there is a considerable amount of lining cloth manufacturing enterprise to select for use other industry to convert the no powder base slurry that is made in a large number even and makes double-point lining cloth, just can't refer to washing fastness and solvent resistance at all with emulsion and water.The influence of cacodoxies such as " no powder base slurry do not participate in bonding effect mechanism only as getting carrier is carrier ready ", or the technician also seldom lets go on producing in some enterprise, and this professional book magazine is also less in addition, comparatively speaking relatively sealing.Do not develop with the development of rag trade but there is powder base slurry over the past two years, the no powder base that the multifunctionality of many middle and high shelves apparel binding fibres be unable to do without tailored version is starched and is realized.
Polyacrylic ester has good scale resistance, weatherability and outstanding oil-proof composition and film-forming properties.But the water-wash resistance and the winter hardiness of polyacrylic ester are poor, the characteristic limitations of its " cold short hot sticky " its utilization in the no powder base of middle and high shelves is starched.When fore portion adhesive lining manufacturers uses no powder base to starch, mostly adopt the common former latex of polypropylene-base of other industry and simply convert sailor worker's labor physics modulation process that is mixed, the dispersion of product, less stable, technology is difficult to control when producing coating operation greatly, and interior quality (anti-dried, washing performance) also can not get guaranteeing simultaneously.
Summary of the invention
Technical problem to be solved by this invention just provides a kind of emulsion polymerization method, the water polyacrylic acid emulsion of its preparation does not have the raw material of powder base slurry with the self-cross linking type water polyacrylic acid as apparel binding fibre, the base slurry latex film of final preparation has good compactness, over-all propertieies such as the adsorption strength of various base materials, water tolerance, solvent resistance are promoted significantly, apply to lining and starch the field, can improve the application performances such as water-fast, anti-solvent of final product lining cloth greatly with no powder base.
For solving the problems of the technologies described above, the present invention adopts following technical scheme: a kind of emulsion polymerization method, before emulsion polymerization, make earlier pre-emulsion and seed emulsion respectively, in the seed emulsion preparation process, used 1/4 pre-emulsion and 1/4 composite initiator, it is characterized in that the emulsion polymerization method comprises the steps:
The nuclear emulsion preparation: the composite initiator solution with 3/4ths is divided into four parts, keep 75 ℃ of temperature of reaction constant, adding first part of composite initiator solution mixes with seed emulsion in reactor, and dropping residue 3/4 pre-emulsion, 1h drips off, and wherein adds second part of composite initiator liquid after 30 minutes;
Shell emulsion preparation: in the disposable adding reactor of the emulsifying agent in the inferior emulsion, add into the 3rd part of composite initiator, drip the monomer of time emulsion then, drip the 4th part of composite initiator after 30 minutes, and finish at the monomer dropping of inferior emulsion and to drip in preceding 20 minutes; Be warming up to 80 ℃, reaction 2h reduces to room temperature, and slowly adds the 10% adipic dihydrazide aqueous solution, is neutralized to pH value=7～8 with ammoniacal liquor, filters, and discharging makes the water polyacrylic acid emulsion.
Preferably, described pre-emulsion is formulated by methyl methacrylate, butyl acrylate, vinylformic acid, diacetone-acryloamide(DAA), alkylamide vinyl sulfonic acid sodium, fatty alcohol-polyoxyethylene ether and deionized water.
Preferably, described seed emulsion is formulated by composite initiator and polymeric kettle bed material, described polymeric kettle bed material is formulated by fatty alcohol-polyoxyethylene ether and deionized water, and described composite initiator is formulated by ammonium persulphate and Sodium dodecylbenzene sulfonate and deionized water.
Preferably, described time emulsion is made up of monomer and emulsifying agent, and described monomer is made up of methyl methacrylate, butyl acrylate, vinylformic acid and diacetone-acryloamide(DAA), and described emulsifying agent is formulated by fatty alcohol-polyoxyethylene ether and deionized water.
The present invention has following advantage:
1, by in system, introducing diacetone-acryloamide(DAA) (DAAM), introduce adipic dihydrazide (ADH) simultaneously and modify side chain, crosslink sites in can the increase system, thereby improve the self-crosslinking performance of water-based PA, warm self-cross linking type base slurry in the formation, can suitably reduce by 10～30 ℃ of baking temperatures, thus but save energy.Even (190 ℃) also not yellowing at high temperature after its film forming has heat-proof aging, cold-resistant, hydrolysis, high anti-particular performances such as after-tack.The more important thing is that to make its performance under the ambient condition of harshness more stable, can make with the curing cross-linked of base cloth, face glue and to combine the tree type reinforcing structure that is huge, generation has the high molecular polymer of high cohesion, makes that bonding force, anti-height are hot, solvent resistance, water tolerance significantly improve.
2, by hydrophobic and hydrophilic monomer are applied to not have powder base slurry through the soap-free emulsion of core-shell emulsion copolymerization technology preparation, make product of the present invention have clean more characteristic at preparation technology, product itself, meet green, environmental protection, health requirements, go with the tide of historical development.In addition,, make in the emulsion particle center DAAM content low because of the present invention adopts core-shell emulsion structure preparation method, DAAM content height in the shell, thus making the surface hardness height, internal layer softish slurry makes that the coating of the finished product lining cloth is soft.
3, by using compound emulsifying agent (reactive emulsifier Em-11, alkylamide vinyl sulfonic acid sodium DNS-86; Nonionic emulsifier, the compound of alkylphenol polyoxyethylene NP) substitutes traditional APEOx type emulsifying agent, participate in the system and carry out copolyreaction with other monomers, between reaction of ionic type emulsifying agent, embedded nonionic emulsifier, on the one hand owing to widened the distance between the reactive emulsifier ion on the emulsion particle surface, on the other hand because the electrostatic shielding effect of nonionic emulsifier, greatly reduce the lip-deep static tension force of emulsion particle, increased the distribution of reactive emulsifier on emulsion particle, thereby can make water-based PA
EmulsionStability improves, its final monodispersity is improved, particle diameter is also less, can obtain the no soap microemulsion of median size at 40～50nm, and possess surface of good tension force, rheological and thixotropy, can guarantee that continuous production does not stop up mesh, and remain the cleanliness factor on cylinder surface, the rounding property of energy holding point type, and make the whole sensory spots type of cloth cover clear.Simultaneously, because of reactive emulsifier Em-11 because of having reactive group such as two keys of C-C, in emulsion polymerization process, be bonded in the middle of the various monomers with more stable covalent, can form finer and close film and adhesivity strong, and reactive group crosslinked offset a part of hydrophilic radical, makes the more conventional latex film of water repelling property of coating outstanding.
4, product of the present invention adopts the neutralizing agent of volatilization amine as system, adds adipic dihydrazide in slurry, keeps neutral when storage at normal temperature, and the ketone carbonyl does not react with hydrazide group.And its when dry because the volatilization of amine, system pH descends, ketone carbonyl and hydrazide group produce crosslinking reaction under the effect of temperature, have farthest guaranteed stability, operability that no powder base is starched.
Embodiment
A kind of apparel binding fibre does not have the preparation method of powder base slurry with the self-cross linking type water polyacrylic acid, comprise the steps: at first, with the water polyacrylic acid emulsion, auxiliary agent mixes with deionized water, wherein, described water polyacrylic acid emulsion is by pre-emulsion, seed emulsion, inferior emulsion, the 10% adipic dihydrazide aqueous solution and ammoniacal liquor are formulated, described pre-emulsion is by methyl methacrylate, butyl acrylate, vinylformic acid, diacetone-acryloamide(DAA), alkylamide vinyl sulfonic acid sodium, fatty alcohol-polyoxyethylene ether and deionized water are formulated, described seed emulsion is formulated by composite initiator and polymeric kettle bed material, described polymeric kettle bed material is formulated by fatty alcohol-polyoxyethylene ether and deionized water, described composite initiator is formulated by ammonium persulphate and Sodium dodecylbenzene sulfonate and deionized water, described time emulsion is made up of monomer and emulsifying agent, described monomer is by methyl methacrylate, butyl acrylate, vinylformic acid and diacetone-acryloamide(DAA) are formed, described emulsifying agent is formulated by fatty alcohol-polyoxyethylene ether and deionized water, and described auxiliary agent comprises whitening agent, sanitas and defoamer; Extremely neutral with ammoniacal liquor regulation system pH value then, add the aqueous acrylic acid series thickening material again and transfer to viscosity＜30000, the condition of this viscosity is mPas/20 ℃.
Preferably, described polyacrylic ester does not have the massfraction of each component in the powder base slurry and is: water polyacrylic acid emulsion 45～48%, aqueous acrylic acid series thickening material 2～3%, auxiliary agent 2～5%, deionized water 45～50%.
Preferably, each ingredients constitute is methyl methacrylate 10～13%, butyl acrylate 8～10%, vinylformic acid 0.25～0.5%, diacetone-acryloamide(DAA) 0.1～0.3%, alkylamide vinyl sulfonic acid sodium 0.5～1.5%, fatty alcohol-polyoxyethylene ether 0.25～0.5%, deionized water 10～11% by the massfraction of water polyacrylic acid emulsion in the described pre-emulsion.
Preferably, each ingredients constitute is a deionized water 42～48% in the deionized water 5～6%, fatty alcohol-polyoxyethylene ether 0.1～2%, polymeric kettle bed material in ammonium persulphate 0.3～0.5%, Sodium dodecylbenzene sulfonate 0.3～0.5%, the composite initiator by the massfraction of water polyacrylic acid emulsion in the described seed emulsion.
Preferably, each ingredients constitute is methyl methacrylate 10～13%, butyl acrylate 7～10%, vinylformic acid 0.5～1%, diacetone-acryloamide(DAA) 0～1%, fatty alcohol-polyoxyethylene ether 0.25～0.5%, deionized water 1～1.5% by the massfraction of water polyacrylic acid emulsion in described emulsion.
Preferably, the compound method of described water polyacrylic acid emulsion is:
1) pre-emulsion preparation drops into each component of pre-emulsion in pre-reactor, is warming up to 55 ℃ and mixes 10min and make pre-emulsion;
2) seed emulsion preparation at first, adds the polymeric kettle bed material and begins stirring, and extract 1/4 pre-emulsion in reactor in reactor, be warming up to 75 ℃, drips 1/4 composite initiator then, and reaction 30min makes seed emulsion;
3) emulsion polymerization,
Nuclear emulsion preparation: remaining 3/4ths composite initiator solution are divided into four parts, keep 75 ℃ of temperature of reaction constant, add first part of composite initiator solution in reactor, and drip residue 3/4 pre-emulsion, 1h drips off, and wherein adds second part of composite initiator liquid after 30 minutes;
Shell emulsion preparation: in the disposable adding reactor of the emulsifying agent in the inferior emulsion, add into the 3rd part of composite initiator, drip the monomer of time emulsion then, drip the 4th part of composite initiator after 30 minutes, and finish at the monomer dropping of inferior emulsion and to drip in preceding 20 minutes; Be warming up to 80 ℃, reaction 2h reduces to room temperature, and slowly adds the 10% adipic dihydrazide aqueous solution, is neutralized to pH value=7～8 with ammoniacal liquor, filters discharging.
The present invention adopts following technical scheme, and a kind of apparel binding fibre does not have powder base slurry with the self-cross linking type water polyacrylic acid, and it is formulated by following component:
| Raw material | Ratio (mass fraction) |
| Water polyacrylic acid (PA) emulsion | 45～48 |
| The aqueous acrylic acid series thickening material | 2～3 |
| Other auxiliary agent | 2～5 |
| Deionized water | 45～50 |
The basic recipe of no powder base slurry also comprises matrix main emulsion, pH value conditioning agent, thickening material, viscosity increaser, whitening agent, sanitas and defoamer etc. except that WATER AS FLOW MEDIUM.Go out the consumption of deionized water and main emulsion by predefined computation schemes, extremely neutral with ammoniacal liquor regulation system pH value, add again after corresponding aqueous promoter transfers to suitable viscosity [viscosity＜30000(mPas/20 ℃)], can prepare product of the present invention, promptly be numbered PRA.
Water polyacrylic acid among the present invention (PA) emulsion is formed by following component reaction:
(1) pre-emulsification proportioning:
(2) preparation of composite initiator:
(3) preparation of polymeric kettle bed material:
(4) second sections raw material monomer proportionings:
(1) pre-emulsification:
With first section monomers methyl methacrylate (MMA), butyl acrylate (BA), vinylformic acid (AA), diacetone-acryloamide(DAA) (DAAM), emulsifying agent and deionized water, drop in proportion in the pre-reactor, be warming up to and mix about 10min about 55 ℃ and make pre-emulsion.
(2) seed emulsion preparation:
In reactor, add deionized water and emulsifying agent fatty alcohol-polyoxyethylene ether, open stirring, and extract 1/4 pre-emulsion in reactor, be warming up to about 75 ℃, drip 1/4 composite initiator solution then, react about 30min, make seed emulsion.
(3) letex polymerization:
The nuclear emulsion preparation: remaining composite initiator solution is divided into four parts, keeps 75 ℃ of temperature of reaction constant, add a composite initiator solution in reactor, and drip residue 3/4 pre-emulsion, 1h drips off, and wherein adds a composite initiator liquid every 30min.
Shell emulsion preparation: second section emulsifying agent is dissolved in the deionized water, and in the disposable adding reactor, add into a initiator liquid, drip second section monomeric mixing solutions then, drip the residue composite initiator after 30 minutes, and finish at second section monomer dropping and to drip in preceding 20 minutes.
Be warming up to 80 ℃, reaction 2h reduces to room temperature, and slowly adds 10% adipic dihydrazide (ADH) aqueous solution, is neutralized to pH value=7～8 with ammoniacal liquor.Filter, discharging obtains a kind of milky emulsion that is blue light, is product of the present invention---and a kind of apparel binding fibre does not have powder base slurry main emulsion with the self-cross linking type water polyacrylic acid.
The used functional monomer of the present invention: diacetone-acryloamide(DAA) (be called for short: DAAM), its structural formula:
Introduce the more than DAAM of ketone carbonyl monomer on the water and milk polymer molecule, other also has (methyl) propenal (aldehyde radical also can form hydrazone with hydrazides and reach crosslinked effect), methyl vinyl ketone, (methyl) vinylformic acid acetoacetoxy groups ethyl ester etc.But DAAM toxicity is little, synthesis material is simple, especially the adhesiveproperties that strengthens slurry is of great benefit to, so the present invention is preferably with the function monomer of DAAM as introduction ketone carbonyl.
The used linking agent of the present invention: adipic dihydrazide (be called for short: ADH), its structural formula:
Crosslinking reaction among the present invention: DMMA participates in the crosslinked simple reaction of emulsion copolymerization and adipic dihydrazide and the ketone carbonyl generation on polymer-modified schematically as follows:
The relational extender of the polymer emulsion of DAAM modification has the hydrazides of binary and polycarboxylic acid, as carbonic acid two hydrazides (CHz), propanedioic acid two hydrazides (MDH), succinic acid hydrazide ii (SDH), adipic dihydrazide (ADH) etc.In general binary and the polynary hydrazides water soluble, the intramolecularly hydrazide group is too not crowded, in order to avoid hinder and the ketone carbonyl reaction.Many hydrazides are more quite a lot of than binary hydrazides interrelating effect, but consider that from aspects such as cost, performances the present invention preferably uses adipic dihydrazide.
Letex polymerization among the present invention and the chemical reaction in the solidification process:
As function monomer, as composite initiator, synthesized the polyacrylate dispersion that contains the ketone carbonyl with diacetone-acryloamide(DAA) (DAAM) with ammonium persulphate-Sodium dodecylbenzene sulfonate.Adopt the neutralizing agent of volatilizable ammoniacal liquor as system, add adipic dihydrazide in slurry, keep neutral when storage at normal temperature, the ketone carbonyl does not react with hydrazide group.And its when dry because the volatilization of amine, system pH reduces, ketone carbonyl and hydrazide group generation crosslinking reaction under the effect of heating, this crosslinking reaction has two characteristics: crosslinked carry out under the middle temperature with the latex drying after take place.DAAM participate in emulsion copolymerization and ADH with polymer-modified on ketone carbonyl generation crosslinking reaction simple reaction schematically as follows:
Reaction 1: with diacetone-acryloamide(DAA) as function monomer, with the copolymerization of ammonium persulphate (APS) and Sodium dodecylbenzene sulfonate (LAS) as the ACRYLIC EMULSION of composite initiator:
Reaction 2: add the linking agent adipic dihydrazide, coating is after bake the cross-linking and curing reaction of generation:
Impose complete, complete, even, full idea on base fabric, this is the basic demand to no powder base slurry coating transfer performance.The principal element that determines its coating performance is the various auxiliary agents in the slurry modulation, wherein thickening material most importantly.The quality of thickening material performance is directly determining the thixotropy, adhesion of slurry etc. and is shifting relevant characteristic.Good thickening material answers usage quantity little and thickening effectiveness is remarkable, and can play a role well in the pH of broad value scope, and thickening product thixotropy is strong, be that product is when being subjected to shear action, its viscosity can descend by a relatively large margin immediately, and in a single day reactive force is eliminated, and its sticky performance is recovered immediately.
Outside the Pass the perviousness of no powder base slurry was removed and had with additive such as thickening material, the tensio-active agent in the system was an important factor.The kind of tensio-active agent and consumption at first want to satisfy the requirement of emulsion polymerization, will look after the penetrating quality of slurry finished product in the future simultaneously, and this is than difficulty.To just might take into account preferably through experiment and screening repeatedly.
In order to satisfy the demand of various special purposes, except requiring to be processed into variform, often must add multiple other reagent and carry out composite.Because the singularity of application is difficult to adopt single compound to meet the demands, so the research of prescription just becomes a crucial factor.The product that adopts compounded technology to release, have functions such as synergy, modification and broadened application scope, its performance often surpasses the single product of structure, so on top of compounded technology is to make lining starch product with no powder base to possess one of good market competition advantage very important channel.In the present invention, by in the investigation starting material to the influence factor of environment, each procedure to no powder base slurry product chain all proposes environmental requirement, science has been selected the non-aqueous system auxiliary rheological agents of ROHM AND HAAS chemical industry and the composite modulation that relevant surfaces coagent (all meeting the strictest environmental requirement of European Union) does not have powder base slurry for use, has obtained beyond thought green ecological technical superiority.
The present invention will be further described below in conjunction with specific embodiment:
The raw material explanation
Methyl methacrylate (MMA), butyl acrylate (BA), vinylformic acid (AA): Dongfang Chemical Plant, Beijing, The East Chemical Plant,Beijing;
Diacetone-acryloamide(DAA) (DAAM): the emerging magnificent chemical industry in Hangzhou company limited;
Adipic dihydrazide (ADH): the emerging magnificent chemical industry in Hangzhou company limited;
Ammonium persulphate (APS): Shanghai chemical reagent factory;
Sodium dodecylbenzene sulfonate (LAS): the Nanjing gold is pleased chemical industry company limited;
Reactive emulsifier Em-11(alkylamide vinyl sulfonic acid sodium DNS-86): deep pool, Shandong intelligence chemical industry company limited;
Non-ionic type (fatty alcohol-polyoxyethylene ether AEO): Zhejiang development of evil in febrile disease group;
Ammoniacal liquor: Shanghai chemical reagent factory;
Deionized water: self-control.
Preparation example 1
The present invention adopts semi-continuous emulsion polymerizing technology, the seeded emulsion polymerization method of pre-emulsified monomer, same prescription is carried out conventional emulsion polymerization and core-shell emulsion polymerization respectively, and the composition to nucleocapsid designs, and has synthesized a series of polymer emulsions, and the prescription composition sees Table 1.
Different polymerization processs of table 1 and prescription are formed
Table 2 is the stability and the emulsion property of different polymerization processs.
The stability of the different polymerization processs of table 2 and emulsion property
Embodiment 1
Get in the preparation example 1 the PRA-2 sample emulsion and reduce to room temperature, and slowly add 10% adipic dihydrazide (ADH) aqueous solution, be neutralized to pH value=7～8 with ammoniacal liquor.Filter, discharging obtains a kind of milky emulsion that is blue light, is product of the present invention---and a kind of apparel binding fibre does not have the main emulsion of powder base slurry with the self-cross linking type water polyacrylic acid.
The basic recipe of no powder base slurry also comprises matrix main emulsion, pH value conditioning agent, thickening material, viscosity increaser, whitening agent, sanitas and defoamer etc. except that WATER AS FLOW MEDIUM.Go out the consumption of deionized water and main emulsion by predefined computation schemes, extremely neutral with ammoniacal liquor regulation system pH value, add again after corresponding aqueous promoter transfers to suitable viscosity [viscosity＜30000(mPas/20 ℃)], can prepare product of the present invention, promptly be numbered PRA.
Getting product of the present invention and polyacrylate(s) both domestic and external among the embodiment 1 does not have powder base slurry and has done a large amount of simultaneous tests of intersecting, and by test, we draw following main testing datas.
At the effect test phase, we have at first selected for use the no powder base slurry of 3 trades mark to compare the sample of test as us, and are wherein external
Italy Bu SaiteProduct grade is DD
3, the farsighted product grade in east, domestic Shanghai is DR-A, product grade of the present invention is PRA.
We have produced four kinds of double-point lining cloths respectively with the no powder base slurry of above 3 trades mark, and the French PA2513 of Atofina is adopted in the upper strata dusting, have selected the low lining base cloth that plays cloth as our sample of 75D for use.
For above 3 kinds of no powder bases slurry, a kind of hot-melt adhesive powder and a kind of base cloth after selecting, we at home certain well-known lining cloth factory carried out coating test, whole production technology is highly stable, each technical parameter also is provided with identical, make the lining cloth sample of 3 classifications respectively, amounted to 3 kinds of lining cloth.We test the washing that above-mentioned 3 kinds of lining cloth have carried out respectively under the various test conditionss.
The glue spread of each sample lining sees the following form 1.
The glue spread information slip of each sample lining of table 1
More than 3 kinds of lining cloth we made the testing experiment (lining: selected 350g/m for use of the stripping strength of seven series respectively
2The jean cloth of medium-thick type is as the test lining; Press the condition of scalding: 135 ℃ * 2.0Kg/cm
2* 18S):
(1) the dry state stripping is strong; The common washing of (2) 40 ℃ * 1h back stripping is strong; (3) 60 ℃ * 1h washing back stripping is strong; (4) 60 ℃ * 3h washing back stripping is strong; Stripping is strong behind (5) 90 ℃ * 1h high temperature stone mill ENZYME WASH; (6) stripping is strong after the dry-cleaning 5 times; (7) stripping is strong after the 30min sand washing.
Concrete test data sees the following form 2.
Each sample lining dry state peel strength test value of table 2
From test case, equally all adopt in dusting under the situation of PA2513, the woven lining that no powder base slurry adopts PRA of the present invention to make does not have powder base slurry from the complete by force esters of acrylic acid that uses in the market that surpasses of dry state stripping.
The common washing of 40 ℃ * 1h back is shelled strong and the conservation rate numerical value of decaying sees the following form 3.
Strong and the conservation rate of decaying of the common washing of 40 ℃ * 1h of table 3 back stripping
By above detection statistics data, after the common washing of 40 ℃ * 1h, the strong and conservation rate of decaying of the stripping of scheme two, three has certain decline; And the conservation rate of decaying of scheme one has surpassed 100%, that is to say, by common washing process, the bonding intensity of lining cloth and lining does not only descend, and a part has on the contrary risen.
60 ℃ * 1h washing back is shelled strong and the conservation rate data that decay see the following form 4.
Strong and the conservation rate of decaying of 60 ℃ * 1h of table 4 washing back stripping
By above detection statistics data, after 60 ℃ * 1h washing, the stripping of scheme two, three is strong and the conservation rate decline that decays is very fast; The conservation rate of decaying of scheme one surpasses 100%, and this explanation scheme one lining cloth is by the washing process of 60 ℃ * 1h, and the washing of these processing condition has certain reinforcement for the bond strength of lining cloth and lining.
Ready-made clothes washing is the general technology of present international fashionable recreation clothes, more natural in order to obtain, comfortable, more have levels, the better clothes of lining stability, usually clothes are washed.ENZYME WASH is exactly a kind of method for washing of using always, and the ferment of ENZYME WASH is a kind of cellulase, and it can be under certain pH value and temperature, fibrous texture is produced Degradation, make cloth cover more leniently to scald look in order to remove hairs, shed (produce " peach skin effect), and obtain lasting soft effect.Common ENZYME WASH will be in 45～55 ℃, the water-bath of pH value 4.5～5.5 about washing 45min, and the ferment deactivation then needs at pH value〉9.0, temperature handle such circulation about 15min in 80 ℃ the water-bath.Strong and the conservation rate numerical value of decaying of stripping sees the following form 5 behind the common ENZYME WASH.
Strong and the conservation rate of decaying of stripping behind the common ENZYME WASH of table 5
By above detection statistics data, situation about obtaining in the production practice check with our routine behind the common ENZYME WASH of scheme two, scheme three is identical substantially, does not have very big variation.Promptly adopt the lining that spins of general homemade base slurry preparation to come off substantially, what do not come off has not had any brute force substantially yet yet.Scheme three decay conservation rate substantially about 50%, that is to say that by the washing process behind the common ENZYME WASH, the bonding intensity of lining cloth and lining has more decline, but the separation strength after the washing is still within standard range.And the conservation rate of decaying of scheme one is still more than 80%, and the anti-common ENZYME WASH ability of explanation scheme one is better.
Strong and the conservation rate numerical value of decaying of stripping sees the following form 6 after dry-cleaning 5 times.
Strong and the conservation rate of decaying of stripping after table 6 is dry-cleaned 5 times
By above detection statistics data, after dry-cleaning 5 times, the stripping of scheme two, scheme three data strong and decay conservation rate and the acquisition in the production practice check of our routine are identical substantially, do not have very big variation; And the conservation rate of decaying of scheme one remains on about 100% substantially, and the anti-dry-cleaning ability of representation scheme one is better.
Strong and the conservation rate numerical value of decaying of stripping sees the following form 7 behind the sand washing 30min.
Strong and the conservation rate of decaying of stripping behind the table 7 sand washing 30min
By above detection statistics data, behind sand washing 30min, the stripping of scheme two, scheme three data strong and decay conservation rate and the acquisition in the production practice check of our routine are identical substantially, do not have very big variation; And the conservation rate of decaying of scheme one is more than 95%, and this illustrates that by the washing flow behind the sand washing 30min bonding intensity of lining cloth and lining has only slight not falling, and the anti-sand washing ability of representation scheme one is better.
From the above, lining cloth and the 350g/m that makes with PA2513 and product P RA of the present invention
2Bonding intensity after the jean coupling of medium-thick type and anti-various washing processing power all are much higher than PA2513 and external DD
3And the lining cloth level made of domestic DR-A.The more general esters of acrylic acid of ability that shows the aspects such as bonding strength, solvent resistance, washable water treatment of product of the present invention does not have powder base slurry and is significantly improved.
What must understand is that preamble is described only to be further to explain to of the present invention.To those skilled in the art, can make different alternativess and improvement without departing from the premise in the spirit of the present invention.Therefore, present invention includes all alternativess and the conversion scheme thereof of its appended claim scope of typing.
Claims (4)
1. emulsion polymerization method, before emulsion polymerization, make earlier pre-emulsion and seed emulsion respectively, in the seed emulsion preparation process, used 1/4 pre-emulsion and 1/4 composite initiator, it is characterized in that the emulsion polymerization method comprises the steps:
The nuclear emulsion preparation: the composite initiator solution with 3/4ths is divided into four parts, keep 75 ℃ of temperature of reaction constant, adding first part of composite initiator solution mixes with seed emulsion in reactor, and dropping residue 3/4 pre-emulsion, 1h drips off, and wherein adds second part of composite initiator liquid after 30 minutes;
Shell emulsion preparation: in the disposable adding reactor of the emulsifying agent in the inferior emulsion, add into the 3rd part of composite initiator, drip the monomer of time emulsion then, drip the 4th part of composite initiator after 30 minutes, and finish at the monomer dropping of inferior emulsion and to drip in preceding 20 minutes; Be warming up to 80 ℃, reaction 2h reduces to room temperature, and slowly adds the 10% adipic dihydrazide aqueous solution, is neutralized to pH value=7～8 with ammoniacal liquor, filters, and discharging makes the water polyacrylic acid emulsion.
2. emulsion polymerization method according to claim 1 is characterized in that: described pre-emulsion is formulated by methyl methacrylate, butyl acrylate, vinylformic acid, diacetone-acryloamide(DAA), alkylamide vinyl sulfonic acid sodium, fatty alcohol-polyoxyethylene ether and deionized water.
3. emulsion polymerization method according to claim 2, it is characterized in that: described seed emulsion is formulated by composite initiator and polymeric kettle bed material, described polymeric kettle bed material is formulated by fatty alcohol-polyoxyethylene ether and deionized water, and described composite initiator is formulated by ammonium persulphate and Sodium dodecylbenzene sulfonate and deionized water.
4. emulsion polymerization method according to claim 3, it is characterized in that: described time emulsion is made up of monomer and emulsifying agent, described monomer is made up of methyl methacrylate, butyl acrylate, vinylformic acid and diacetone-acryloamide(DAA), and described emulsifying agent is formulated by fatty alcohol-polyoxyethylene ether and deionized water.
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