CN102558577B - Method for preparing PVC (polyvinyl chloride) plastisol containing butyronitrile rubber - Google Patents
Method for preparing PVC (polyvinyl chloride) plastisol containing butyronitrile rubber Download PDFInfo
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- CN102558577B CN102558577B CN2011104286521A CN201110428652A CN102558577B CN 102558577 B CN102558577 B CN 102558577B CN 2011104286521 A CN2011104286521 A CN 2011104286521A CN 201110428652 A CN201110428652 A CN 201110428652A CN 102558577 B CN102558577 B CN 102558577B
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J3/00—Processes of treating or compounding macromolecular substances
- C08J3/18—Plasticising macromolecular compounds
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/0008—Organic ingredients according to more than one of the "one dot" groups of C08K5/01 - C08K5/59
- C08K5/0016—Plasticisers
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L9/00—Compositions of homopolymers or copolymers of conjugated diene hydrocarbons
- C08L9/02—Copolymers with acrylonitrile
- C08L9/04—Latex
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2327/00—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Derivatives of such polymers
- C08J2327/02—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Derivatives of such polymers not modified by chemical after-treatment
- C08J2327/04—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Derivatives of such polymers not modified by chemical after-treatment containing chlorine atoms
- C08J2327/06—Homopolymers or copolymers of vinyl chloride
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2409/00—Characterised by the use of homopolymers or copolymers of conjugated diene hydrocarbons
- C08J2409/02—Copolymers with acrylonitrile
- C08J2409/04—Latex
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Abstract
The invention belongs to the technical field of chemical industry, and in particular relates to a method for preparing PVC (polyvinyl chloride) plastisol containing butyronitrile rubber. The method comprises the following steps of: dispersing butyronitrile latex into a plasticizer DINP (diisononyl phthalate) in a proportion according to steps; adding a surfactant to stabilize the system to obtain a stable aqueous polymer dispersing system; and adding the prepared stable aqueous polymer dispersing system in PVC plastisol to obtain the PVC plastisol product containing the butyronitrile rubber. According to the invention, when the PVC plastisol is prepared by using the method, the problem that the aqueous polymer additive is difficultly mixed into the PVC plastisol is solved. By using the method, the dispersion of the polymer is fine, and the polymer is prevented from caking.
Description
Technical field
The present invention relates to a kind of method for preparing the pvc plastisol that includes butadiene-acrylonitrile rubber, belong to chemical technology field.
Background technology
During the pvc plastisol that contains other polymkeric substance in preparation, the very large challenge faced is to be difficult to polymkeric substance is fully sneaked in pvc plastisol.Fully mix generally need to be longer time, or promote the shearing stress of mixed system, these at high temperature carry out usually, like this can the reverse influence polymkeric substance.There will be and mixing difficult phenomenon is that polymkeric substance can lump because while being added in softening agent (or plastisol) by polymkeric substance, and polymkeric substance is dissolved in softening agent and forms and has high polymers concentration and full-bodied regional area.Be coated with more low viscous softening agent around these regional areas.As everyone knows, it is very difficult full-bodied liquid being sneaked into to low-viscosity (mobile) liquid.To mixture, provide shearing force just can form the mixing dropping liquid that is coated another kind of liquid by a kind of liquid.By checking the degree that dropping liquid is elongated or being subject to the degree of crushing of shearing force can determine the degree of its mixing.It is because the liquid around full-bodied flowing fluid ratio is more easily covert that high viscosity liquid is difficult to sneak in low-viscosity (mobile) liquid.
Summary of the invention
The technical problem to be solved in the present invention is to provide a kind of method for preparing the pvc plastisol that includes butadiene-acrylonitrile rubber, and it has overcome while preparing pvc plastisol (or pvc plastisol itself) and is difficult to polymeric additive is sneaked into to the problem in softening agent.The method can make polymer dispersed more meticulous, and can prevent the polymer formation caking.
For solving the problems of the technologies described above, the present invention is achieved by the following technical solutions:
A kind of method for preparing the pvc plastisol that includes butadiene-acrylonitrile rubber of the present invention, it comprises the following steps:
Nitrile rubber is scattered in softening agent DINP in proportion, then add tensio-active agent and nitrile rubber (dry weight) mass ratio 0.01-0.2: 1 stablizes above system, obtain stable aqueous polymer dispersions system, then be to be added in pvc plastisol by above aqueous polymer dispersions, obtain the pvc plastisol product that contains butadiene-acrylonitrile rubber;
Described nitrile rubber, softening agent DINP, tensio-active agent and pvc plastisol are 1: 5 by weight: (0.01-0.2): (3-10);
Described tensio-active agent is a kind of in sorbitan mono-oleic acid ester or sorbitol monostearate.
Preferably, described preparation includes the method for the pvc plastisol of butadiene-acrylonitrile rubber, and the HLB value of wherein said tensio-active agent is 3.5-6.
Preferably, described preparation includes the method for the pvc plastisol of butadiene-acrylonitrile rubber, and described nitrile rubber is a kind of in paracril latex HT108, paracril latex HT208 or nitrile rubber.
Preferably, described preparation includes the method for the pvc plastisol of butadiene-acrylonitrile rubber, and described aqueous polymer dispersions is, was first dewatered before preparing pvc plastisol.
Preferably, described preparation includes the method for the pvc plastisol of butadiene-acrylonitrile rubber, and described nitrile rubber and softening agent DINP (diisononyl phthalate) are 1: 5 in mass ratio.
Preferably, described preparation includes the method for the pvc plastisol of butadiene-acrylonitrile rubber, and the compound method of described pvc plastisol comprises the following steps:
A. taking the softening agent DINP (diisononyl phthalate) of 126.06g and the viscosity-depression agent TXIB of 50.25g (name is called 2,2,4-trimethylammonium-1, the two isobutyrates of 3-pentanediol) joins in beaker and stirs 15 minutes;
B. in the situation that in stirring the 239.75gPVC powder being joined to aforesaid liquid gradually, stir, rotating speed 700-1000 rev/min, 1.5 adding the weight of tranquilizer CZ-115 after hour is that 3.31g (being accurate to 0.01g) stirs 30 minutes again, obtain pvc plastisol, tested viscosity and fineness after 2 hours, logging test results is standby.
Preferably, described preparation includes the method for the pvc plastisol of butadiene-acrylonitrile rubber, and it also comprises the oil-in-water emulsification of softening agent DINP (diisononyl phthalate), and concrete steps are:
A. taking 342.7g softening agent DINP (diisononyl phthalate) joins in clean beaker;
B. take 13.7g tensio-active agent S-80 (oleic acid sorbitol ester) and join in the beaker that fills softening agent DINP (diisononyl phthalate), obtain mixed solution;
C. with stirrer, the mixed solution of step b is fully stirred 30 minutes, temperature 25 degree, then add latex 157.5g, and stir, obtain water base softening agent DINP (diisononyl phthalate) emulsion that contains nitrile rubber.
Preferably, described preparation includes the method for the pvc plastisol of butadiene-acrylonitrile rubber, it also comprises the mixing of water base softening agent emulsion and pvc plastisol, concrete steps are: take water base softening agent DINP (diisononyl phthalate) emulsion of respective amount in the situation that in stirring and joining slowly the pvc plastisol prepared, in the situation that 25 ℃ of slowly stirring observations overnight have or not layering.
The beneficial effect that the present invention compared with prior art has is:
The present invention is difficult to polymeric additive is sneaked into to the problem in described softening agent while by described polymkeric substance being made an addition in described softening agent with the form with the immiscible dispersions with low viscosity of described softening agent, having overcome, preparing pvc plastisol (or pvc plastisol itself).This method can make described polymer dispersed more meticulous, and can prevent described polymer formation caking.
And described polymkeric substance adds with the form of latex, described latex is the aqueous dispersion with meticulous polymer particle, and has lower viscosity.The low viscosity of latex make its can rapid dispersion in described softening agent (or plastisol).Described polymkeric substance will still be disperseed and is interrupted with water form independently because of polymkeric substance in the increase of the solvability in continuous softening agent stage and consequent whole system viscosity.We also can utilize surface active material to strengthen the stability of softening agent (latex) and the relative mixture that immiscible polymeric dispersions produces with it.
Embodiment
Below in conjunction with embodiment, the present invention is described in further detail.
Polyvinyl chloride, usually referred to as PVC, is a kind of thermoplastic polymer of widespread use.In many fields, polyvinyl chloride often mixes use with softening agent.Except polyvinyl chloride resin and softening agent, plasticity PVC compound also comprises thermo-stabilizer usually, also can comprise other selectable components, for example tinting material, fire retardant, static inhibitor, lubricant, ultra-violet stabilizer, fluid regulation agent and filler.Being added into softening agent in described PVC compound can make by the second-order transition temperature that reduces polymeric matrix described PVC more soft and be rich in toughness.If use sufficient softening agent, its second-order transition temperature can be reduced to below room temperature.These highly plasticized property PVC are rubber-based products, can be applicable to multiple fields, comprise wire coating, toy, clothes, flexible pipe, intravenous infusion bag and gloves.
High-ductility PVC compound is usually processed with the form of pvc plastisol or " paste ".Pvc plastisol is the meticulous PVC powder lot dispersing body (sometimes also relating to " dispersion resin " or " paste resin " rank) that is dissolved in the continuous plasticising stage.This is a unsure state of PVC-plasticiser mixture in thermodynamics.The steady state of the described PVC plasticiser mixture of thermodynamics refers to the plasticity polymeric matrix of homogeneous phase.Pvc plastisol has a larger using value industrial, and this is because it has kinetic stability, and under environment usually, softening agent needs long time to mix with PVC mutually.When in the system of place, independently solid phase dispersion is in continuous liquid phase, pvc plastisol starts to occur fluid deformation.When the plasticity polymkeric substance as polyvinyl chloride resin with softening agent when molecular level mixes, the PVC-plasticiser mixture starts to occur fluid deformation.It is extremely quick that at high temperature this transformation can occur.Therefore by heat effect, the pvc plastisol of liquid state or pasty state can fast transition be the solid polymer matrix.
As everyone knows, industrially often softening agent and PVC are used jointly.Representative softening agent for PVC has phthalic ester, benzoic ether, trioctyl trimellitate, phosphoric acid ester, dicarboxylic acid alkyl ester, low-molecular-weight polymeric ester class (being generally molecular weight between 800-4000) and Epoxy oil.Selecting party mask at softening agent has some important standards.The softening agent that any system is used, some important standards comprise anti-performance, toxicity, combustibility and the smell of overflowing in volatility, the validity (reducing the validity of the second-order transition temperature aspect of PVC) as softening agent, mechanical property, application.Very important point is that used softening agent should easily mix with utilization ratio and the selected PVC progression of use temperature according to softening agent in addition.If the two incompatible softening agent that will cause oozes out from polymkeric substance.All the time, with the common maximum softening agent used of PVC, be phthalic ester.
Many Application Areass attempt adding other polymkeric substance in plasticity PVC compound to form blend polymer, and achieve success.For example add the blend of paracril or synthetic chloroprene rubber polymer and incite somebody to action flexible more than independent liquid plasticity PVC, can improve some character of gained blend, for example low temperature flexibility, friction resistant and resistance to cleavage and oil resistant and fuel performance simultaneously.In pvc plastisol, use these polymkeric substance also to have difficulties, while especially in described blend, having used high-molecular weight polymer.This is because during the pvc plastisol that contains other polymkeric substance in preparation, is difficult to described polymkeric substance is fully sneaked into to described plastisol.Fully mix generally need to be longer time, or make mixture be subject to higher can the described polymkeric substance shearing force of reverse impact.This situation is because, when polymkeric substance is added in softening agent (or plastisol), polymkeric substance almost is dissolved in softening agent immediately, and formation has high polymers concentration and full-bodied regional area; And other described polymkeric substance of great majority do not show the fluid stability to polyvinyl chloride resin while mixing with described softening agent yet.Be coated with more low viscous softening agent around the regional area of these high polymers concentration.As everyone knows, it is very difficult full-bodied liquid being sneaked into to low-viscosity (mobile) liquid.To mixture, provide shearing force just can form the mixing dropping liquid that is coated another kind of liquid by a kind of liquid.By checking the degree that dropping liquid is elongated or being subject to the degree of crushing of shearing force can determine the degree of its mixing.It is because the liquid resistance to deformation more around full-bodied flowing fluid ratio that high viscosity liquid is difficult to sneak in low-viscosity (mobile) liquid.
Usually, pure polymkeric substance is added in softening agent and fully and dissolve.Aqueous polymer dispersions or latex are seldom used, and this is because it did not mix mutually and can not form stable mixture with softening agent in the water stage; The mixture thereupon produced also can fast decoupled.The invention provides a kind of using polymkeric substance as aqueous dispersion or latex be added into the mode of softening agent.Surprisingly, method of the present invention also obtains stable mixture and has obvious advantage than the method that directly polymkeric substance is added into to softening agent.The present invention adds polymkeric substance as the water dispersion agent, and is suitable for forming the surface dispersant of stable water-in-oil emulsion by use, with overcome with softening agent between do not mix mutually.Tensio-active agent can stabilizing plasticizer and the separation surface in water stage, makes the rapid emulsification of described polymer emulsion and sneaks into described softening agent.Along with polymkeric substance continues to be scattered in water stage of latex, described polymkeric substance can better disperse in described softening agent.Make in this way described polymer dispersed, overcome low-viscosity (mobile) liquids such as high-viscosity polymer being scattered in to softening agent and the difficulty that produces.
Tensio-active agent by stablize two not the separation surface between mixed phase play a role.Originally immiscible two-phase more easily makes two-phase be uniformly dispersed after adding tensio-active agent.Decreasing by surfactant the energy of two intersection interfaces, make and be more prone to form interface region, and form the meticulousr disperse phase of fineness of dispersion.In addition, tensio-active agent also will infiltrate described separation surface, and make dispersion more stable by hindering polymer polymerizing and de-emulsification.All used tensio-active agent in many Application Areass.Negatively charged ion, positively charged ion, non-ionic group and amphotericeledrolyte are the main tensio-active agents of four classes.Every class tensio-active agent all has more wide in range type of service and chemical constitution.Due to the diversity of selectable tensio-active agent, people are just making great efforts to attempt the molecules character of caluclate table surface-active agent.A kind of system extensively be used is that the hydrophile-lyophile balance system is the HLB system.This is the lipophilicity of a test molecule or the empirical method of hydrophilicity.Each tensio-active agent all defines the value of 0 (entirely oil-wet molecule) to 20 (total hydrophilic molecules).Usually use our initial option of HLB systematic direction to demonstrate the tensio-active agent of different surfaces activity.For the aqueous-based polymers dispersion be scattered in softening agent or pvc plastisol, its objective is and create out a kind of water-in-oil emulsion.Research finds that the tensio-active agent of HLB value between 3.5 to 6 contributes to stablize water-in-oil emulsion usually.The HLB value of many tensio-active agents is all in this scope.Sorbitan monooleate (HLB=3.7) for example, stearin (HLB=3.8), Yelkin TTS (HLB=4), sorbitol monooleate (HLB=4.3), sorbitan monostearate (HLB=4.7), emulsifying agent steareth-2 (HLB=4.9), Brij oleth-2 (HLB=4.9), glycerine lauric acid (HLB=5.2), Diethylene Glycol list margaron ceteth-2 (HLB=5.3), PEG-30 dimerization hydroxy stearic acid ester (HLB=5.5), stearin (HLB=5.8), PEG-4 dilaurate (HLB=6).
Have been found that nitrile rubber polymer can be used as the additive use of plasticity PVC compound.Paracril is the multipolymer of acrylonitrile and butadiene.The content that in the paracril of commercial level, propylene is fine is 18-50%.In mineral oil and non-polar solvent, paracril shows good thermotolerance and anti-swelling property, and paracril is mainly used as the specialty elastomer that needs these character.The hydro carbons tolerance of paracril class is the fine polarity of propylene come from multipolymer.This polarity also makes paracril and the PVC compound compatibility of many progression and is suitable for the compound with PVC.Paracril prepares by letex polymerization usually.The paracril latex thereupon produced is usually through supersolidification with process the dry rubber substance for the production of sheet, tabular, chip form and powder type, but many paracrils with the form of latex for special applications.Paracril latex generally contains the dry rubber substance of 30-60% content, the stable particle form that wherein polymkeric substance is steric configuration, and described particle is scattered in water with the progression of 100 nanometers.
It is no matter dry paracril or paracril latex all can not be easy to mix with softening agent and for the preparation of pvc plastisol.The invention provides a kind of tensio-active agent that is suitable for setting up acrylonitrile-butadiene rubber latex by use in the PVC softening agent, can easily paracril latex be sneaked into to the method for pvc plastisol.Unexpectedly, found the stable emulsion form of paracril latex in softening agent by this kind of mode, and paracril latex can not decompose in softening agent in emulsified effect.The result that paracril latex is dispersed in softening agent can be considered as a kind of composite emulsion, and described composite solution is particle stabilized being scattered in water of paracril, and paracril particle itself also forms stable dispersion in softening agent.This situation originates from the relative dimension of paracril particle and aqueous phase dispersibility.Emulsion can be defined as a kind of liquid dispersion in another kind of liquid and immiscible form.The size of dispersion particle is between the hundreds of nanometer is to several microns (document 6).In between particle size and particle volume, existing cubic relationship, one drops in the latex of emulsification in softening agent, its particle size is 1 micron level, the paracril particle that wherein to include many particle sizes be 100 Nano grades, this is because volume is 1000 times of level calculation with particle size.
Following embodiment is not in order to limit the scope of the invention, but the specific embodiment of the present invention will be described fully.
Embodiment 1
The preparation of water base softening agent DINP (diisononyl phthalate) emulsion
Prepare a series of water dispersions that can be in dinonyl, DINP (diisononyl phthalate), and by apparent its stability of assessment of scenario that is separated of observing.The design parameter of these water dispersions refers to table 1.Prepare water base softening agent DINP emulsion, the first step is that tensio-active agent S-80 (oleic acid sorbitol ester) is dissolved in softening agent DINP (diisononyl phthalate), along with continuous stirring and by specific water base nitrile rubber, slowly adds in softening agent DINP (diisononyl phthalate) surfactant mixture.Stir 15 minutes, standing overnight, observe the layering situation.
When selecting sorbitol monostearate as tensio-active agent, softening agent DINP (diisononyl phthalate) need to be heated to 65 ℃ of ability and dissolve described tensio-active agent.Selected water base nitrile rubber is HT108, HT208, or any in Latex A.Described three kinds of latex all have three-dimensional conformation stability, and contain about 43.5% solids fraction.The paracril latex that HT108 and HT208 paracril are carboxylic esterification, and the vinyl cyanide component concentration is all higher, and can buy in the Shijiazhuang safe rubber of letter company business.LatexA is a kind of non-esterization paracril, and contains 28% vinyl cyanide component.
Embodiment 2
At first paracril latex is scattered in softening agent DINP (diisononyl phthalate) and makes the solution that paracril and softening agent DINP (diisononyl phthalate) ratio are 1: 5, then remove water.
By 229.78 gram Latex A (containing 43.52% solids fraction) be added into continuous stirring in the solution of 500 gram softening agent DINP (diisononyl phthalate) and 20 gram tensio-active agent S-80 (oleic acid sorbitol ester) preparation more than 30 minutes.Consequently latex forms emulsion in the external phase of softening agent DINP (diisononyl phthalate).Described emulsion, by constantly stirring and thermal dehydration, makes described emulsion form 40 ℃ of homogeneous phase solutions that viscosity is 30000cps.
Comparative Examples 1
Prepare by dry paracril being scattered in softening agent DINP (diisononyl phthalate) solution that paracril and softening agent DINP (diisononyl phthalate) ratio are 1: 5.
Latex A is solidified in ethanol, and in vacuum chamber 80 ℃ the gained coagulum is dried to constant weight, make the dry rubber substance sample.Get the above-mentioned dry rubber substance of 100g and be crushed to fritter and be added in 500g softening agent DINP (diisononyl phthalate), make required dry rubber substance solution.Softening agent DINP (diisononyl phthalate) and rubber stock are heated to 96 ℃ and stir 48 hours, make described rubber reach its molten point and make described solution avoid forming agglomerating particles.The viscosity that gained solution is 40 ℃ is 54000cps.
Water base softening agent DINP (diisononyl phthalate) emulsion prepared by the condition in above Comparative Examples 1, the technique of employing is loaded down with trivial details, and consumes energy is high, and operational condition requires high, is not suitable for suitability for industrialized production.
Embodiment 3
The consumption of adjustment sheet surface-active agent S-80 (oleic acid sorbitol ester)
By 229.78 gram Latex A (containing 43.52% solids fraction) be added into continuous stirring in the solution of 500 gram softening agent DINP (diisononyl phthalate) and 10 gram tensio-active agent S-80 (oleic acid sorbitol ester) preparation more than 30 minutes.Consequently latex forms emulsion in the external phase of softening agent DINP (diisononyl phthalate).Described emulsion, by constantly stirring and thermal dehydration, makes described emulsion form 40 ℃ of homogeneous phase solutions that viscosity is 48000cps.
Embodiment 4
Prepare pvc plastisol
Taking the softening agent DINP (diisononyl phthalate) of 180g and the viscosity-depression agent TXIB of 45.6g (name is called 2,2,4-trimethylammonium-1, the two isobutyrates of 3-pentanediol) joins in beaker and stirs 15 minutes; In the situation that in stirring the 200gPVC powder being joined to aforesaid liquid gradually, stir, rotating speed 700-1000 rev/min, 1.5 add tranquilizer CZ-115 (calcium zinc soap salt) 3.00g (being accurate to 0.01g) to stir again after hour 30 minutes, obtain pvc plastisol, after 2 hours, the viscosity of test is 205cps, and fineness is 78um.
Embodiment 5
Preparation is sneaked in pvc plastisol and water-free plasticity PVC film by paracril
Use water base softening agent DINP (diisononyl phthalate) emulsion prepared in embodiment 2 and Comparative Examples 1 to prepare the pvc plastisol that contains paracril, and prepare plasticity PVC film.Paracril latex/softening agent DINP (diisononyl phthalate) solution is heated to 40 ℃, along with continuous stirring adds softening agent DINP (diisononyl phthalate), viscosity-depression agent TXIB and PVC powder successively, make required pvc plastisol.Mix after 1.5 hours, add tranquilizer CZ-115 (calcium zinc soap salt) in PVC sticks with paste, and additionally stir 30 minutes.Be applied in after plastisol is degassed on two sheet glass, and be positioned in 210 ℃ of baking ovens and dry 8 minutes, obtain two plasticity PVC films that contain paracril.The film cooling cooling made also can be shifted out from sheet glass.Regulate 23 ℃ of temperature, the relative humidity 39% of film, and measure the tensile property of film.Resulting film consumption and tensile property have been listed in table 2.The standby film of the ownership system is all transparent.
TXIB is a kind of extender plasticizer used in these compounds, and its name is called 2,2,4-trimethylammonium-1, the two isobutyrates of 3-pentanediol.The polyvinyl chloride resin used is LP170G.The stablizer used is CZ-115.
Embodiment 6
Preparation is sneaked in pvc plastisol and moisture plasticity PVC film by paracril
12g oleic acid sorbitol ester S-80 is dissolved in 300g softening agent DINP (diisononyl phthalate), then add 137.865g paracril latex HT108 emulsification more than 20 minutes, nitrile rubber can be scattered in softening agent DINP (diisononyl phthalate).Along with continuous stirring is added 86.51g viscosity-depression agent TXIB in dispersion liquid, continue to stir after 10 minutes and add again the 192gPVC resin.Stir after 1.5 hours and add 5.19g tranquilizer CZ-115, then the continuation stirring makes the required pvc plastisol that contains nitrile rubber in 30 minutes.
Getting the above plastisol of 7g is layed on ceramic plate and makes described film.Be positioned over 210 ℃ of baking ovens 10 minutes.The film obtained is spumescence, and film is but that transparence whole film have been full of small bubbles.
Claims (8)
1. a method for preparing the pvc plastisol that includes butadiene-acrylonitrile rubber, is characterized in that, it comprises the following steps:
By nitrile rubber, be scattered in proportion in diisononyl phthalate, then add tensio-active agent and nitrile rubber mass ratio and be 0.01 ?0.2:1 stablize above system, obtain stable aqueous polymer dispersions system, then be to be added in pvc plastisol by described aqueous polymer dispersions, obtain the pvc plastisol product that contains butadiene-acrylonitrile rubber;
Described nitrile rubber, diisononyl phthalate, tensio-active agent and pvc plastisol be by weight 1:5:(0.01 ?0.2): (3 ?10);
Described tensio-active agent is a kind of in sorbitan mono-oleic acid ester or sorbitol monostearate.
2. preparation as claimed in claim 1 includes the method for the pvc plastisol of butadiene-acrylonitrile rubber, it is characterized in that, the HLB value of wherein said tensio-active agent is 3.5-6.
3. preparation as claimed in claim 1 includes the method for the pvc plastisol of butadiene-acrylonitrile rubber, it is characterized in that, described nitrile rubber is a kind of in paracril latex HT108 or paracril latex HT208.
4. preparation as claimed in claim 1 includes the method for the pvc plastisol of butadiene-acrylonitrile rubber, it is characterized in that, described aqueous polymer dispersions is, was first dewatered before preparing pvc plastisol.
5. preparation as claimed in claim 1 includes the method for the pvc plastisol of butadiene-acrylonitrile rubber, it is characterized in that, described nitrile rubber and diisononyl phthalate are 1:5 in mass ratio.
6. preparation as claimed in claim 1 includes the method for the pvc plastisol of butadiene-acrylonitrile rubber, it is characterized in that, the compound method of described pvc plastisol comprises the following steps:
A. take the diisononyl phthalate of 126.06g and 50.25g viscosity-depression agent 2,2,4 ?San Jia Ji ?1,3 ?the two isobutyrates of pentanediol join in beaker and stir 15 minutes;
B. in the situation that in stirring the 239.75gPVC powder being joined to aforesaid liquid gradually, stir, rotating speed 700 ?1000 rev/mins, 1.5 after hour, add tranquilizer CZ ?115 weight be 3.31g, stir again 30 minutes, obtain pvc plastisol, tested viscosity and fineness after 2 hours, logging test results is standby.
7. preparation as claimed in claim 1 includes the method for the pvc plastisol of butadiene-acrylonitrile rubber, it is characterized in that, it also comprises the oil-in-water emulsification of diisononyl phthalate, and concrete steps are:
A. taking the 342.7g diisononyl phthalate joins in clean beaker;
B. take 13.7g tensio-active agent oleic acid sorbitol ester and join in the beaker that fills diisononyl phthalate, obtain mixed solution;
C. with stirrer, the mixed solution of step b is fully stirred 30 minutes, temperature 25 degree, then add latex 157.5g, and stir, obtain the water base diisononyl phthalate emulsion that contains nitrile rubber.
8. preparation as claimed in claim 1 includes the method for the pvc plastisol of butadiene-acrylonitrile rubber, it is characterized in that, it also comprises the mixing of water base diisononyl phthalate emulsion and pvc plastisol, concrete steps are: take the water base diisononyl phthalate emulsion of respective amount in the situation that in stirring and joining slowly the pvc plastisol prepared, in the situation that 25 ℃ of slowly stirring observations overnight have or not layering.
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| CN110885510B (en) * | 2019-12-04 | 2021-10-08 | 宿迁市南京工业大学新材料研究院 | Water dispersion system plasticized PVC resin and preparation method thereof |
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| US4595617A (en) * | 1984-05-31 | 1986-06-17 | Gencorp Inc. | Carpet tiles having a filled flexible frothed vinyl polymer backing and their method of manufacture |
| CN1184136A (en) * | 1996-11-18 | 1998-06-10 | 固特异轮胎和橡胶公司 | Plastisol composition |
| CN101608102A (en) * | 2009-07-06 | 2009-12-23 | 华南理工大学 | A kind of PVC resin adhesive for ceramics and preparation method thereof |
| CN101990560A (en) * | 2007-12-21 | 2011-03-23 | 埃克森美孚化学专利公司 | Co-plasticizer systems |
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Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4595617A (en) * | 1984-05-31 | 1986-06-17 | Gencorp Inc. | Carpet tiles having a filled flexible frothed vinyl polymer backing and their method of manufacture |
| CN1184136A (en) * | 1996-11-18 | 1998-06-10 | 固特异轮胎和橡胶公司 | Plastisol composition |
| CN101990560A (en) * | 2007-12-21 | 2011-03-23 | 埃克森美孚化学专利公司 | Co-plasticizer systems |
| CN101608102A (en) * | 2009-07-06 | 2009-12-23 | 华南理工大学 | A kind of PVC resin adhesive for ceramics and preparation method thereof |
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