CN110819024A - Method for improving dispersity of PVC impact modifier in polymerization process - Google Patents

Method for improving dispersity of PVC impact modifier in polymerization process Download PDF

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Publication number
CN110819024A
CN110819024A CN201810901903.5A CN201810901903A CN110819024A CN 110819024 A CN110819024 A CN 110819024A CN 201810901903 A CN201810901903 A CN 201810901903A CN 110819024 A CN110819024 A CN 110819024A
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Prior art keywords
impact
acr
mass
improving
dispersibility
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CN201810901903.5A
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张振国
张海瑜
冯智刚
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Yanya Branch Of Shandong Ruifeng Polymer Materials Co Ltd
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Yanya Branch Of Shandong Ruifeng Polymer Materials Co Ltd
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Priority to CN201810901903.5A priority Critical patent/CN110819024A/en
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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
    • C08L27/00—Compositions 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; Compositions of derivatives of such polymers
    • C08L27/02—Compositions 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; Compositions of derivatives of such polymers not modified by chemical after-treatment
    • C08L27/04—Compositions 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; Compositions of derivatives of such polymers not modified by chemical after-treatment containing chlorine atoms
    • C08L27/06—Homopolymers or copolymers of vinyl chloride
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
    • C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
    • C08F220/10—Esters
    • C08F220/12—Esters of monohydric alcohols or phenols
    • C08F220/14—Methyl esters, e.g. methyl (meth)acrylate
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2205/00—Polymer mixtures characterised by other features
    • C08L2205/03—Polymer mixtures characterised by other features containing three or more polymers in a blend

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  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Graft Or Block Polymers (AREA)
  • Polymerisation Methods In General (AREA)

Abstract

The invention belongs to the field of preparation of ACR (acrylic resin) additives, and particularly relates to a method for improving dispersibility of a PVC (polyvinyl chloride) impact modifier in a polymerization process. The invention is scientific, reasonable, simple and easy to implement, the impact strength of the processing aid with high molecular weight is little influenced by the method through tests, the dispersity of the processing aid is greatly improved, and the fluidity and the processing performance of PVC can be improved and the addition amount of the processing aid in the original formula can be reduced due to the addition of the high molecular processing aid.

Description

Method for improving dispersity of PVC impact modifier in polymerization process
Technical Field
The invention belongs to the field of preparation of ACR (acrylic rubber) auxiliaries, and particularly relates to a method for improving dispersibility of a PVC impact modifier in a polymerization process.
Background
Polyvinyl chloride is widely used as a general-purpose plastic for a wide range of applications, and is widely used in various fields due to its excellent mechanical properties and low price. However, since the PVC resin itself has disadvantages of poor thermal stability, poor low temperature resistance, poor fluidity, insufficient toughness, etc., various additives are added to improve its properties. Compared with other impact modifiers, the acrylate impact modifier has good processing performance and obvious impact resistance effect; the product has beautiful surface and excellent weather resistance; the variety and the number are multiple, and the application is wide. In the early 80 s, Okubo, a Japanese scholars, proposed a new concept of "particle design", further promoting the development of core-shell structure acrylate copolymers. So far, the core-shell structure polymeric modifier has been the focus of research, and the research on synthesis, structure, performance and the like has been greatly advanced.
The impact modifier has the main functions of improving the normal-temperature and low-temperature brittleness and mechanical strength of the PVC resin, promoting the melting process of the PVC resin and improving the rheological property. The impact modifier is mainly used in PVC hard products and semi-hard products, and the market of the impact modifier for PVC shows two vigorous trends of production and sale along with the development of PVC building material industry and the continuous widening of application fields. Among them, the ACR type impact modifier having a core-shell structure has attracted attention and developed rapidly due to its advantages such as excellent toughness, good weather resistance, good moldability, beautiful appearance of the product, high dimensional accuracy, and maintaining of the optimum impact strength over a wide range of use temperatures.
The acrylic ester impact modifier is a high molecular polymer with a core/shell structure, namely a core/shell structure polymer which takes a crosslinked acrylic ester rubbery polymer as a core and takes an acrylic ester plastic polymer as a shell. The structure and size of the core/shell modifier is determined during the synthesis process, and due to the nature of the components of the outer layer, the particles remain unchanged after being dispersed in the matrix resin, while the final structural morphology and size of the linear polymer and bulk rubber blended with the matrix resin is affected by the processing conditions. The core-shell structure modifier has a given particle size and a narrow size distribution, and can be optimally designed from the structural aspect, so that the core/shell structure modifier is a more ideal impact modifier.
The core/shell composition ratio is an important parameter affecting the performance of ACR toughened and modified PVC. On one hand, when the content of the core component is low, the modifier is mainly composed of hard monomer components, so that the silver streak initiation, branching and termination rates are reduced, and the ideal toughening modification effect cannot be achieved. On the other hand, when the core content is high, the shell component can not completely wrap the shell component, so that a complete core/shell structure can not be formed, and because the core viscosity of the rubber phase is high, latex particles are easy to adhere and agglomerate due to partial exposure during emulsion breaking, so that the latex particles can not be uniformly dispersed in PVC, and the ideal toughening purpose can not be achieved. Suitable core/shell composition ratios will depend on the monomer composition of the core shell in the particular system.
If the problem of poor dispersion cannot be solved, on one hand, the product can be agglomerated, and particularly in areas with high temperature, the agglomeration is serious, so that the transportation of the product is inconvenient; on the other hand, when the PVC material is used for producing PVC products, the PVC material is difficult to disperse uniformly in the mixing process, so that the product quality is unstable, and a plurality of problems are generated to cause production interruption.
Disclosure of Invention
The invention aims to provide a method for improving the dispersibility of the impact-resistant ACR auxiliary agent, which is scientific, reasonable, simple and feasible, and greatly improves the dispersibility of the impact-resistant ACR auxiliary agent; when the PVC modifier is applied to PVC, the fluidity and the processing performance of the PVC are improved, and the addition amount of a processing aid in the original formula is reduced.
The method for improving the dispersibility of the impact-resistant ACR auxiliary agent comprises the following steps:
(1) adding water into a reaction container, introducing nitrogen, adding a polymerization monomer, a molecular weight regulator and an emulsifier, stirring, adding an initiator for reaction, preserving heat after the reaction is finished, and cooling to obtain a high molecular weight polymer emulsion;
(2) and adding the obtained high molecular weight polymer emulsion into the impact-resistant ACR emulsion, stirring, spraying and drying to obtain the acrylic resin emulsion.
The polymerization monomer in the step (1) is one or more of acrylate monomers, styrene or acrylonitrile.
The acrylic ester monomer is one or more of methyl methacrylate, ethyl methacrylate, propyl methacrylate, butyl methacrylate or butyl acrylate.
The molecular weight regulator in the step (1) is one of dodecyl mercaptan, isooctyl 3-mercaptopropionate, tert-dodecyl mercaptan, tetramentacene tetraethanol tetrakis (3-mercaptopropionate) or ethyl hexanol 3-mercaptopropionate.
The emulsifier in the step (1) is one of sodium dodecyl sulfate, sodium dodecyl benzene sulfonate, sodium dodecyl sulfonate, sodium didodecyl phenyl ether disulfonate or sodium polyoxyethylene ether sulfate.
The initiator in the step (1) is one of potassium persulfate, ammonium persulfate or cumene hydroperoxide.
In the step (1), the total mass of water and the polymerized monomer is 100 percent by mass, and the ratio is as follows:
58 to 68 percent of water
32-42% of polymerized monomer.
The mass of the emulsifier in the step (1) is 0.4-3% of the mass of the polymerized monomer, the mass of the molecular weight regulator is 0.001-0.05% of the mass of the polymerized monomer, and the mass of the initiator is 0.01-0.1% of the mass of the polymerized monomer.
The reaction temperature in the step (1) is 55-80 ℃, the heat preservation temperature is 75-80 ℃, the heat preservation time is 1-3 hours, and the temperature is reduced to 35-50 ℃.
The stirring time in the step (1) is 0.5 to 2 hours.
The mass of the pure material of the high molecular weight polymer emulsion in the step (2) is 5-20% of that of the impact-resistant ACR emulsion, the pure material of the high molecular weight polymer emulsion refers to the residual part of the high molecular weight polymer emulsion after drying, and the pure material of the impact-resistant ACR emulsion refers to the residual part of the impact-resistant ACR emulsion after drying.
The stirring time in the step (2) is 0.5 to 2 hours.
The ACR impact modifier is prepared by a step polymerization method of seed emulsion polymerization. The method has the advantages that the composition, the size, the shell thickness, the ratio of the radius of the shell layer to the radius of the core layer, the surface functional characteristics and the like of the particles can be controlled according to different requirements in the synthesis reaction process, and the obtained particles have uniform size distribution. According to the method, after the synthesis of the impact resistant ACR and before demulsification, a polymer processing aid synthesized by one or more of acrylates, styrene or acrylonitrile is added, so that the materials are fully mixed and dispersed, and then spraying is carried out to obtain the product.
The invention adopts water as a medium, forms a better emulsion phase by adding a corresponding emulsifier, can ensure that monomers can be uniformly dispersed in the medium, and adopts peroxide as an initiator to prepare the high molecular polymer emulsion with the viscosity range of 3-7. And then fully mixing the ACR emulsion with the mixture, and then carrying out spray drying to obtain well-dispersed ACR powder particles.
Compared with the prior art, the invention has the following beneficial effects:
the invention is scientific, reasonable, simple and easy to implement, the processing aid with high molecular weight is firstly prepared, the trichloromethane is used as a solvent, the viscosity is within the range of 3-7, the trichloromethane is added into the impact resistant ACR for mixing, the impact strength of the processing aid is slightly influenced, the dispersity of the processing aid is greatly improved, meanwhile, the macromolecular processing aid is added, the fluidity and the processing performance of the PVC can be improved, and the addition amount of the processing aid in the original formula is reduced.
Detailed Description
The present invention is further described below with reference to examples.
Example 1
(1) Adding 400g of water into a reaction vessel, introducing nitrogen, adding 240g of methyl methacrylate, 60g of butyl acrylate, 0.005g of dodecyl mercaptan and 3.0g of sodium dodecyl sulfate, stirring for 0.5 hour, adding 0.21g of potassium persulfate at 58 ℃ for reaction, keeping the temperature at 80 ℃ for 1 hour after the reaction is finished, and cooling to 50 ℃ to obtain high-molecular-weight polymer emulsion;
(2) adding the obtained high molecular weight polymer emulsion into 3450g of impact-resistant ACR emulsion, fully stirring for 2 hours, spraying and drying to obtain the acrylic latex.
The product obtained in this example is compared with the use of the raw material impact ACR used in this example for PVC articles, and the product obtained in this example contains 92% of pure impact ACR, but the impact strength is only reduced by 2.2%; the product obtained in this example has a strength of 7.6% higher than that obtained by increasing the shell of the ACR raw material used in this example by 8%, and the plasticization of the product is better than that of the latter.
Example 2
(1) Adding 400g of water into a reaction container, introducing nitrogen, adding 220g of methyl methacrylate, 60g of styrene, 0.002g of 3-isooctyl mercaptopropionate and 3.2g of sodium dodecyl sulfate, stirring for 2 hours, adding 0.25g of ammonium persulfate at 60 ℃ for reaction, keeping the temperature at 75 ℃ for 2 hours after the reaction is finished, and cooling to 35 ℃ to obtain high-molecular-weight polymer emulsion;
(2) adding the obtained high molecular weight polymer emulsion into 2520g of impact-resistant ACR emulsion, fully stirring for 0.5 hour, spraying and drying to obtain the acrylic latex.
The product obtained in this example is compared with the use of the raw material impact ACR used in this example for PVC articles, and the product obtained in this example contains 90% of pure impact ACR, but the impact strength is only reduced by 2.5%; the product obtained in this example has a strength of 8.4% higher than that obtained by increasing the shell of the ACR raw material used in this example by 10%, and the plasticization of the product is better than that of the latter.
Example 3
(1) Adding 380g of water into a reaction container, introducing nitrogen, adding 120g of styrene, 60g of acrylonitrile, 140g of methyl methacrylate, 0.007g of tert-dodecyl mercaptan and 5.0g of sodium dodecyl benzene sulfonate, stirring for 1 hour, adding 0.35g of cumene hydroperoxide at 63 ℃ for reaction, keeping the temperature at 78 ℃ for 3 hours after the reaction is finished, and cooling to 45 ℃ to obtain high molecular weight polymer emulsion;
(2) adding the obtained high molecular weight polymer emulsion into 1680g of impact-resistant ACR emulsion, fully stirring for 1 hour, spraying and drying to obtain the acrylic latex.
The product obtained in this example is compared with the use of the raw material impact ACR used in this example for PVC articles, and the product obtained in this example contains 84% of pure impact ACR, but the impact strength is only reduced by 4.8%; the product obtained in this example, compared with the 16% increase in the shell of the ACR impact material used in this example, has a strength of 8.9% and a better plasticization than the latter.
Although the invention has been described in detail with respect to the general description and the specific embodiments, it will be apparent to those skilled in the art that modifications and improvements can be made thereto without departing from the spirit of the invention.

Claims (10)

1. A method for improving dispersibility of a PVC impact modifier in a polymerization process is characterized by comprising the following steps:
(1) adding water into a reaction container, introducing nitrogen, adding a polymerization monomer, a molecular weight regulator and an emulsifier, stirring, adding an initiator for reaction, preserving heat after the reaction is finished, and cooling to obtain a high molecular weight polymer emulsion;
(2) and adding the obtained high molecular weight polymer emulsion into the impact-resistant ACR emulsion, stirring, spraying and drying to obtain the acrylic resin emulsion.
2. The method for improving the dispersibility of an impact ACR aid according to claim 1, wherein the polymerized monomer in the step (1) is one or more of acrylate monomers, styrene or acrylonitrile.
3. The method for improving the dispersibility of an impact ACR aid according to claim 2, wherein the acrylate monomer is one or more of methyl methacrylate, ethyl methacrylate, propyl methacrylate, butyl methacrylate, or butyl acrylate.
4. The method of claim 1, wherein the molecular weight modifier in step (1) is one of dodecyl mercaptan, isooctyl 3-mercaptopropionate, tert-dodecyl mercaptan, quaternary cyclopentadienyl tetraol tetrakis (3-mercaptopropionate), or ethyl hexanol 3-mercaptopropionate.
5. The method for improving the dispersibility of an impact ACR aid according to claim 1, wherein the emulsifier in step (1) is one of sodium lauryl sulfate, sodium dodecylbenzenesulfonate, sodium dodecylsulfonate, sodium didodecylphenyl ether disulfonate, or sodium polyoxyethylene ether sulfate.
6. The method of improving the dispersibility of an impact ACR aid according to claim 1, wherein said initiator in step (1) is one of potassium persulfate, ammonium persulfate, or cumene hydroperoxide.
7. The method for improving the dispersibility of the impact-resistant ACR aid according to claim 1, wherein in the step (1), the ratio is as follows, wherein the mass percentage is calculated by taking the total mass of water and the polymerized monomer as 100%:
58 to 68 percent of water
32-42% of polymerized monomer.
8. The method for improving the dispersibility of an impact ACR aid according to claim 1, wherein the mass of the emulsifier in step (1) is 0.4 to 3% of the mass of the polymerized monomer, the mass of the molecular weight modifier is 0.001 to 0.05% of the mass of the polymerized monomer, and the mass of the initiator is 0.01 to 0.1% of the mass of the polymerized monomer.
9. The method for improving the dispersibility of an impact-resistant ACR aid according to claim 1, wherein the reaction temperature in step (1) is 55-80 ℃, the holding temperature is 75-80 ℃, the holding time is 1-3 hours, and the temperature is reduced to 35-50 ℃.
10. The method of claim 1 wherein the high molecular weight polymer emulsion of step (2) has a solids mass of from 5 to 20% of the solids mass of the impact ACR emulsion.
CN201810901903.5A 2018-08-09 2018-08-09 Method for improving dispersity of PVC impact modifier in polymerization process Pending CN110819024A (en)

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CN201810901903.5A CN110819024A (en) 2018-08-09 2018-08-09 Method for improving dispersity of PVC impact modifier in polymerization process

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN201810901903.5A CN110819024A (en) 2018-08-09 2018-08-09 Method for improving dispersity of PVC impact modifier in polymerization process

Publications (1)

Publication Number Publication Date
CN110819024A true CN110819024A (en) 2020-02-21

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Application publication date: 20200221