CN116162315A - Polyvinyl chloride paste resin and preparation method thereof - Google Patents

Polyvinyl chloride paste resin and preparation method thereof Download PDF

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Publication number
CN116162315A
CN116162315A CN202310329288.6A CN202310329288A CN116162315A CN 116162315 A CN116162315 A CN 116162315A CN 202310329288 A CN202310329288 A CN 202310329288A CN 116162315 A CN116162315 A CN 116162315A
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Prior art keywords
polyvinyl chloride
paste resin
chloride paste
preparation
polymer
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张建君
刘书霞
田鹏
郭孝伟
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Jining Zhongyin Electrochemical Co ltd
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Jining Zhongyin Electrochemical Co ltd
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    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08KUse of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K9/00Use of pretreated ingredients
    • C08K9/04Ingredients treated with organic substances
    • C08K9/06Ingredients treated with organic substances with silicon-containing compounds
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08FMACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F214/00Copolymers 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
    • C08F214/02Monomers containing chlorine
    • C08F214/04Monomers containing two carbon atoms
    • C08F214/06Vinyl chloride
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08KUse of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K7/00Use of ingredients characterised by shape
    • C08K7/22Expanded, porous or hollow particles
    • C08K7/24Expanded, porous or hollow particles inorganic
    • C08K7/26Silicon- containing compounds
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08KUse of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K9/00Use of pretreated ingredients
    • C08K9/10Encapsulated ingredients
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08KUse of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K2201/00Specific properties of additives
    • C08K2201/011Nanostructured additives

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  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
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Abstract

The invention relates to the field of high polymer materials, in particular to a polyvinyl chloride paste resin and a preparation method thereof, wherein the polyvinyl chloride paste resin provided by the invention has 93-95% of vinyl chloride as a main component, so as to ensure that the paste resin has higher polymerization degree and stability, is used for producing high-quality polyvinyl chloride products, and can improve the fluidity and viscosity of the paste resin and improve the processability by adding a proper amount of cross-linking agent, emulsifying agent, viscosity regulator and solvent; the preparation method provided by the application has the advantages of simple process flow and easiness in preparation, can prevent the phenomena of overpolymerization and sticking paste through step polymerization, ensures the controllability and the repeatability of the polymerization reaction, shortens the reaction time and improves the reaction efficiency, and the prepared material has excellent performance, so that the preparation method can be used for manufacturing various applications including artificial leather, wallpaper, conveying belts, disposable PVC gloves and the like.

Description

Polyvinyl chloride paste resin and preparation method thereof
Technical Field
The invention relates to the technical field of high polymer materials, in particular to a polyvinyl chloride paste resin and a preparation method thereof.
Background
The polyvinyl chloride paste resin is one of polyvinyl chloride resins. The PVC glove is widely applied to various fields such as artificial leather, wallpaper, conveyor belts, disposable PVC gloves and the like.
The paste viscosity of the polyvinyl chloride paste resin directly affects the processing and quality of the product at the rear end, if the paste viscosity is too high, the plasticizer consumption is large, the production cost is high, the product stability can be affected, the mechanical property and the transparency of the product are poor, and the defoaming property of the paste resin with lower paste viscosity is poor, so that the appearance and the quality of the product are affected.
Therefore, the application aims at providing the polyvinyl chloride paste resin with good mechanical property and processability and the preparation method thereof.
Disclosure of Invention
In order to solve the problems, the invention provides a polyvinyl chloride paste resin and a preparation method thereof, so as to provide the polyvinyl chloride paste resin with good mechanical property and processability, and better solve the technical problems.
The technical scheme adopted by the invention is as follows:
the polyvinyl chloride paste resin comprises the following components in percentage by mass:
Figure BDA0004154364770000011
Figure BDA0004154364770000021
further, the fatty alcohol is a mixture of cetyl alcohol and stearyl alcohol in a mass ratio of 1:3.
Further, the composite viscosity modifier is prepared from the following components in percentage by mass: 1 and Brij 58.
Further, the pH buffer is phosphate or carbonate.
Further, the terminator is mercaptoethanol.
Further, the modified SiO 2 Is nano silicon dioxide with surface carboxyl modified.
Further, the surface carboxyl modified nano silicon dioxide is carboxyl modified silane composite nano silicon dioxide or carboxyl modified polymer coated nano silicon dioxide.
Based on the same inventive concept, the present application also provides a method for preparing the polyvinyl chloride paste resin described above, comprising the following preparation steps:
s1, preparing materials according to mass proportions;
s2, adding pure water, potassium sulfate, part of sodium dodecyl sulfate and a pH buffer into a polymerization kettle, vacuumizing, adding vinyl chloride monomer in a stirring state, introducing nitrogen, heating, and performing polymerization reaction to obtain a polymer A;
s3, mixing fatty alcohol, diethylene glycol dimethacrylate, dicumyl peroxide and the rest of sodium dodecyl sulfate, adding the mixture into the polymer A, homogenizing, and then introducing nitrogen into a polymerization kettle and heating to perform polymerization reaction to obtain a polymer B;
s4, mixing the polymer B, the composite adhesion promoter, the terminator and the modified SiO 2 Adding the mixture into a mixing kettle, mixing under the stirring condition, and then performing spray drying and grinding to obtain a finished product.
Further, in the step S2, after nitrogen is introduced, the pressure is controlled to be 0.1-0.2MPa, and the temperature is raised to 45-50 ℃;
in the step S3, the homogenization time is 2-3h, after nitrogen is introduced, the pressure is controlled to be 0.15-0.25MPa, and the temperature is raised to 45-50 ℃;
in the step S4, stirring and blending are carried out for 1-1.5h.
Further, in the step S4, the spraying pressure is 0.3-0.4MPa, the air flow is 8-10L/min, the drying temperature is 65-75 ℃ and the drying time is 10-15min.
The beneficial effects of the invention are as follows:
1. the polyvinyl chloride paste resin provided by the invention has 93-95% of chloroethylene as a main component, ensures higher polymerization degree and stability of the paste resin, is used for producing high-quality polyvinyl chloride products, can improve the fluidity and viscosity of the paste resin and improve the processing performance by adding a proper amount of cross-linking agent, emulsifying agent, viscosity modifier and solvent, can shorten the reaction time and improve the reaction efficiency by taking dicumyl peroxide and potassium sulfate as polymerization catalysts, can improve the yield and reduce the cost, can effectively prevent the phenomena of superpolymerization and sticking paste by adding a terminator, ensures the controllability and repeatability of the polymerization reaction, and particularly has the functions of the solvent and the cross-linking agent, wherein the potassium sulfate is matched for cross-linking, and the use of dicumyl peroxide can improve the rate and the emulsification effect of the polymerization reaction, and reduce the use amount of the emulsification aid, and can interact with cations on the surface of the resin to prevent the penetration and swelling of the plasticizer on resin particles, thereby effectively reducing the use amount of the plasticizer for SiO of the later plasticizer by using the modified resin 2 The polymer has good hydrophilicity, so that the dispersibility and compatibility of the polymer in the polymer can be improved, the stability of the material can be further improved, and the quality stability of the rear end product can be ensured;
2. the preparation method provided by the application has the advantages of simple process flow and easiness in preparation, can prevent the phenomena of overpolymerization and sticking paste through step polymerization, ensures the controllability and the repeatability of the polymerization reaction, shortens the reaction time and improves the reaction efficiency, and the prepared material has excellent performance, so that the preparation method can be used for manufacturing various applications including artificial leather, wallpaper, conveying belts, disposable PVC gloves and the like.
Drawings
Fig. 1 is a block diagram of a flow chart for preparing a polyvinyl chloride paste resin in an embodiment of the present application.
Detailed Description
In order that the invention may be understood more fully, a more particular description of the invention will be rendered by reference to the embodiments that are illustrated below. This invention may, however, be embodied in many different forms and should not be construed as limited to the embodiments set forth herein. Other embodiments obtained by modifying or equally replacing the technical scheme of the invention without creative results are all within the protection scope of the invention.
Unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs. The terminology used in the description of the invention herein is for the purpose of describing particular embodiments only and is not intended to be limiting of the invention.
The values disclosed in the embodiments of the present invention are approximate values and are not determined values. Where the error or experimental conditions allow, all values within the error range may be included without limiting the specific values disclosed in the embodiments of the present invention.
Unless otherwise specifically indicated, the various raw materials, reagents, instruments, equipment and the like used in the present invention are commercially available or may be prepared by existing methods.
Example 1
The embodiment provides a polyvinyl chloride paste resin, which comprises the following components in percentage by mass:
Figure BDA0004154364770000041
example 2
Figure BDA0004154364770000042
Figure BDA0004154364770000051
Example 3
Figure BDA0004154364770000052
Referring to fig. 1, the polyvinyl chloride paste resins described in examples 1 to 3 were prepared as follows:
comprises the following preparation steps:
s1, preparing materials according to mass proportions;
s2, adding pure water, potassium sulfate, 1/2 sodium dodecyl sulfate and a pH buffer agent into a polymerization kettle, vacuumizing, adding vinyl chloride monomer under stirring, introducing nitrogen, controlling the pressure to be 0.1MPa, heating to 50 ℃, and performing polymerization reaction to obtain a polymer A;
s3, mixing fatty alcohol, diethylene glycol dimethacrylate, dicumyl peroxide and the rest of sodium dodecyl sulfate, adding into the polymer A, homogenizing, introducing nitrogen into a polymerization kettle, controlling the pressure to be 0.15MPa, and heating to 50 ℃; heating and carrying out polymerization reaction to obtain a polymer B;
s4, mixing the polymer B, the composite adhesion promoter, the terminator and the modified SiO 2 Adding into a mixing kettle, mixing for 1h under stirring, spray drying under the spray pressure of 0.3MPa, air flow of 8L/min, drying at 72deg.C for 12min, and grinding to obtain the final product.
The polyvinyl chloride paste resins of examples 1 to 3 were subjected to particle size, polymerization degree and tackiness test, and auxiliaries were added to prepare test pieces, and performance test was performed
Figure BDA0004154364770000061
The polyvinyl chloride paste resin provided by the invention has the main component of vinyl chloride, the content of which is 93-95%, so as to ensure that the paste resin has higher polymerization degree and stability, is used for producing high-quality polyvinyl chloride products, and can improve the fluidity and viscosity of the paste resin and the processability by adding proper amount of cross-linking agent, emulsifying agent, viscosity regulator and solventThe cumene and the potassium sulfate are used as polymerization catalysts, the reaction time can be shortened, the reaction efficiency can be improved, the yield can be improved, the cost can be reduced, the addition of the terminator can effectively prevent the phenomena of superpolymerization and sticking, the controllability and the repeatability of the polymerization reaction can be ensured, in particular, the diethylene glycol dimethacrylate has the functions of a solvent and a cross-linking agent, the potassium sulfate is matched for cross-linking, the use of the dicumyl peroxide can improve the rate and the emulsification effect of the polymerization reaction, the use amount of an emulsification auxiliary agent can be reduced, the use of the composite tackifier can interact with cations on the surface of the resin, the permeation and the swelling of the plasticizer on resin particles can be prevented, and the use amount of the plasticizer in the later stage can be effectively reduced by using modified SiO 2 The polymer has good hydrophilicity, can improve the dispersibility and compatibility in the polymer, further improve the stability of the material and ensure the quality stability of the rear end product.
The foregoing examples illustrate only a few embodiments of the invention and are described in detail herein without thereby limiting the scope of the invention. It should be noted that it will be apparent to those skilled in the art that several variations and modifications can be made without departing from the spirit of the invention, which are all within the scope of the invention. Accordingly, the scope of protection of the present invention is to be determined by the appended claims.

Claims (10)

1. The polyvinyl chloride paste resin is characterized by comprising the following components in percentage by mass:
Figure FDA0004154364660000011
2. the polyvinyl chloride paste resin as claimed in claim 1, wherein the fatty alcohol is a mixture of cetyl alcohol and stearyl alcohol in a mass ratio of 1:3.
3. The polyvinyl chloride paste resin according to claim 1, wherein the composite tackifier is in a mass ratio of 2-3:1 and Brij 58.
4. The polyvinyl chloride paste resin of claim 1, wherein the pH buffering agent is a phosphate or carbonate.
5. The polyvinyl chloride paste resin as claimed in claim 1, wherein the terminator is mercaptoethanol.
6. The polyvinyl chloride paste resin as recited in claim 1, wherein said modified SiO 2 Is nano silicon dioxide with surface carboxyl modified.
7. The polyvinyl chloride paste resin as recited in claim 6, wherein the surface carboxyl-modified nano silica is carboxyl-modified silane composite nano silica or carboxyl-modified polymer coated nano silica.
8. A process for preparing the polyvinyl chloride paste resin as defined in any one of claims 1 to 7, comprising the following preparation steps:
s1, preparing materials according to mass proportions;
s2, adding pure water, potassium sulfate, part of sodium dodecyl sulfate and a pH buffer into a polymerization kettle, vacuumizing, adding vinyl chloride monomer in a stirring state, introducing nitrogen, heating, and performing polymerization reaction to obtain a polymer A;
s3, mixing fatty alcohol, diethylene glycol dimethacrylate, dicumyl peroxide and the rest of sodium dodecyl sulfate, adding the mixture into the polymer A, homogenizing, and then introducing nitrogen into a polymerization kettle and heating to perform polymerization reaction to obtain a polymer B;
s4, mixing the polymer B, the composite adhesion promoter, the terminator and the modified SiO 2 Adding the mixture into a mixing kettle, mixing under the stirring condition, and then performing spray drying and grinding to obtain a finished product.
9. The method for producing a polyvinyl chloride paste resin as claimed in claim 8, wherein,
in the step S2, after nitrogen is introduced, the pressure is controlled to be 0.1-0.2MPa, and the temperature is raised to 45-50 ℃;
in the step S3, the homogenization time is 2-3h, after nitrogen is introduced, the pressure is controlled to be 0.15-0.25MPa, and the temperature is raised to 45-50 ℃;
in the step S4, stirring and blending are carried out for 1-1.5h.
10. The method for producing a polyvinyl chloride paste resin according to claim 8, wherein in step S4, the spray pressure is 0.3 to 0.4MPa, the air flow rate is 8 to 10 liters/minute, the drying temperature is 65 to 75 ℃, and the drying time is 10 to 15 minutes.
CN202310329288.6A 2023-03-30 2023-03-30 Polyvinyl chloride paste resin and preparation method thereof Pending CN116162315A (en)

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Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101851308A (en) * 2009-04-03 2010-10-06 中国科学院化学研究所 In-situ suspension polymerization preparation method of nanocomposite material consisting of polyvinyl chloride and silicon dioxide and product thereof
CN102952229A (en) * 2011-08-26 2013-03-06 沈阳化工股份有限公司 PVC (Polyvinyl Chloride) paste resin and preparation method thereof
KR20130090309A (en) * 2012-02-03 2013-08-13 주식회사 엘지화학 Viscosity reducing agent for paste vinyl chloride resins and and method for controlling viscosity of paste vinyl chloride resin using thereof
CN109970902A (en) * 2019-02-03 2019-07-05 唐山三友氯碱有限责任公司 The production method of dulling polyvinyl chloride paste resin
CN113698517A (en) * 2021-06-17 2021-11-26 济宁中银电化有限公司 Polyvinyl chloride paste resin and preparation method thereof

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101851308A (en) * 2009-04-03 2010-10-06 中国科学院化学研究所 In-situ suspension polymerization preparation method of nanocomposite material consisting of polyvinyl chloride and silicon dioxide and product thereof
CN102952229A (en) * 2011-08-26 2013-03-06 沈阳化工股份有限公司 PVC (Polyvinyl Chloride) paste resin and preparation method thereof
KR20130090309A (en) * 2012-02-03 2013-08-13 주식회사 엘지화학 Viscosity reducing agent for paste vinyl chloride resins and and method for controlling viscosity of paste vinyl chloride resin using thereof
CN109970902A (en) * 2019-02-03 2019-07-05 唐山三友氯碱有限责任公司 The production method of dulling polyvinyl chloride paste resin
CN113698517A (en) * 2021-06-17 2021-11-26 济宁中银电化有限公司 Polyvinyl chloride paste resin and preparation method thereof

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