CN112778452B - Preparation method of strong-core toughening agent for PVC (polyvinyl chloride) foam board - Google Patents
Preparation method of strong-core toughening agent for PVC (polyvinyl chloride) foam board Download PDFInfo
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- CN112778452B CN112778452B CN202110129324.5A CN202110129324A CN112778452B CN 112778452 B CN112778452 B CN 112778452B CN 202110129324 A CN202110129324 A CN 202110129324A CN 112778452 B CN112778452 B CN 112778452B
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- 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
- C08F220/16—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms
- C08F220/18—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms with acrylic or methacrylic acids
- C08F220/1812—C12-(meth)acrylate, e.g. lauryl (meth)acrylate
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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
- C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
- C08J9/0061—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof characterized by the use of several polymeric components
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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
- C08J2433/00—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 only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Derivatives of such polymers
- C08J2433/04—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 only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Derivatives of such polymers esters
- C08J2433/06—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 only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Derivatives of such polymers esters of esters containing only carbon, hydrogen, and oxygen, the oxygen atom being present only as part of the carboxyl radical
- C08J2433/10—Homopolymers or copolymers of methacrylic acid esters
Abstract
The invention discloses a preparation method of a strong core toughening agent for a PVC (polyvinyl chloride) foaming plate, which belongs to the technical field of PVC processing aid production, wherein an inorganic material and other raw material monomers are organically combined by emulsion polymerization to obtain a linear long molecular chain toughening agent with an inorganic matter and an organic matter organically combined, the toughening agent is added into a PVC foaming hard product and can be uniformly dispersed into the PVC foaming hard product in a molten state to form a network structure, so that the compatibility of the toughening agent and the PVC foaming hard product is increased, the core layer hardness of the PVC foaming hard product is improved, the nail holding force of the product is improved, the product competitiveness is improved, the application of the PVC foaming hard product is promoted, the production process is equivalent to that of a PVC foaming regulator, the production improvement investment is reduced, and the industrial production can be realized.
Description
Technical Field
The invention relates to the technical field of PVC processing aid production, in particular to a preparation method of a strong core toughening agent for a PVC foam board.
Background
The PVC foam board is also called as a PVC snowboard and an Andi board, takes polyvinyl chloride (PVC) as a main raw material, is added with various auxiliaries, and is a novel green and environment-friendly material. At present, the PVC industry develops rapidly and has wide prospects all over the world, all countries see the potential of PVC and the benefit of PVC on ecological environment, and the excellent and unique performance of PVC proves to the world that the function and status of PVC cannot be replaced by any other products at present. The PVC foaming board is widely applied to industries of ship and train manufacturing, furniture manufacturing, decoration and fitment, silk screen printing of advertising industry, manufacturing and the like, has far better processing performance than wood when being processed in the same way as wood, and is an ideal substitute for wood, aluminum materials and composite boards.
The PVC foaming board has the performance advantages of heat insulation, sound insulation, flame retardance, stable chemical performance, weather resistance, water resistance, moth prevention and the like, has good secondary processing performance, can be sawed, nailed, planed, drilled and bonded, has no pollution to the environment, can be recycled, and is a green and environment-friendly product. Compared with other plastic products, the composite material has the advantages of light unit weight, high outturn percentage, capability of reducing the resin content of the product in unit volume and reduction in the production cost of the product. At the end of the 90 s of the 20 th century, foreign literature has discussed that plastic wood-like materials have been identified as good substitutes for wood, and no other similar materials can be substituted in the next 50 years.
Along with the popularization of the application of PVC foamed products, particularly hard products, the strength, mechanical requirements and the like of the PVC foamed products are continuously improved, the problem that the core layer strength of the existing PVC foamed hard products is low generally exists, and the application and popularization of the PVC foamed hard products are also limited.
Disclosure of Invention
In order to solve the technical problems, the invention provides a preparation method of a strong core toughening agent for a PVC (polyvinyl chloride) foamed plate, which is characterized in that an inorganic material and other raw material monomers are organically combined by emulsion polymerization to obtain a linear long molecular chain toughening agent with an inorganic matter and an organic matter organically combined, and after the toughening agent is added into a PVC foamed hard product, the hardness of a core layer of the PVC foamed hard product can be greatly improved, the nail holding power of the product is improved, and the application of the PVC foamed hard product is popularized.
In order to achieve the purpose, the technical scheme adopted by the invention is as follows:
a preparation method of a strong core toughening agent for a PVC foam board comprises the following steps:
(1) adding 200 parts by weight of 150-50 ℃ of monomer, 150 parts by weight of 100-150 ℃ of water, 2-5 parts by weight of emulsifier, 1.5-4 parts by weight of cross-linking agent, 0.15-1.6 parts by weight of dispersant, 0.02-0.08 part by weight of wetting agent, 1.5-3 parts by weight of inorganic material and 0.03-0.25 part by weight of pH regulator into a reaction kettle, discharging oxygen by using nitrogen, starting stirring, controlling the rotating speed to be 100-50 ℃ at 200r/min, and heating to 45-50 ℃;
(2) when the temperature of the emulsion is constant at 45-50 ℃, adding 0.25-0.5 weight part of initiator in total, cooling to 35-40 ℃, continuing stirring for reaction, and controlling the reaction time of the emulsion for 5-18 h;
(3) heating to 75 ℃, curing for 1-2h, then cooling to 35 ℃, discharging to obtain copolymer emulsion;
(4) and demulsifying, washing and drying the prepared copolymer emulsion to obtain powdery emulsion particles.
Preferably, the monomer consists of hydroxypropyl acrylate and lauryl methacrylate, and the mass ratio of the hydroxypropyl acrylate to the lauryl methacrylate is 1: 2.
Preferably, the emulsifier is a composite emulsifier consisting of sodium dodecyl sulfate and polyethylene glycol octyl phenyl ether (OP-10).
Preferably, the cross-linking agent is any one or more of GMA, allyl phthalate, vinyltriethoxysilane, vinyltrimethoxysilane and vinyltris (beta-methoxyethoxy) silane.
Preferably, the dispersant is sodium dihydrogen phosphate.
Preferably, the wetting agent is one or two of sodium dodecyl sulfate and sodium dodecyl benzene sulfonate.
Preferably, the pH adjusting agent is sodium bicarbonate.
Preferably, the initiator is a redox initiator, wherein the reducing agent is sodium dithionite and the oxidizing agent is di-tert-butyl peroxide (DTBP), or the initiator is any one of potassium persulfate and ammonium persulfate.
Preferably, the inorganic material is any one of magnesium sulfate whisker, calcium carbonate whisker, glass fiber and calcium sulfate whisker.
The beneficial effects of the invention are as follows:
1. according to the invention, inorganic materials and other raw material monomers are organically combined by emulsion polymerization, so that a linear long molecular chain flexibilizer with an organically combined inorganic matter and organic matter is obtained, and the flexibilizer is added into a PVC (polyvinyl chloride) foamed hard product and can be uniformly dispersed into the PVC foamed hard product in a molten state to form a network structure, so that the compatibility of the flexibilizer and the PVC foamed hard product is increased, the hardness of a core layer of the PVC foamed hard product is improved, the nail holding power of the product is improved, the product competitiveness is improved, and the application of the PVC foamed hard product is promoted;
2. the toughening agent can replace part of PVC foaming regulator, reduces the addition of the PVC foaming regulator in the PVC foaming hard product, has a production process equivalent to that of the PVC foaming regulator, reduces the production improvement investment, and can realize industrial production.
Detailed Description
To facilitate understanding of those skilled in the art, the present invention will be further described with reference to specific examples:
example 1:
a preparation method of a strong core toughening agent for a PVC foam board comprises the following steps:
(1) adding 150 parts by weight of monomer, 100 parts by weight of water, 2 parts by weight of emulsifier, 1.5 parts by weight of cross-linking agent, 0.15 part by weight of dispersant, 0.02 part by weight of wetting agent, 1.5 parts by weight of magnesium sulfate whisker and 0.03 part by weight of pH regulator into a reaction kettle, discharging oxygen by nitrogen, starting stirring, controlling the rotating speed to be 100 plus 200r/min, and heating to 45-50 ℃;
(2) when the temperature of the emulsion is constant at 45-50 ℃, adding 0.25 weight part of initiator in total amount, continuing stirring for reaction, and controlling the reaction time of the emulsion for 5-18 h;
(3) heating to 75 ℃, curing for 1-2h, then cooling to 35 ℃, discharging to obtain copolymer emulsion;
(4) and demulsifying, washing and drying the prepared copolymer emulsion to obtain powdery emulsion particles.
The monomer consists of hydroxypropyl acrylate and lauryl methacrylate, and the mass ratio of the hydroxypropyl acrylate to the lauryl methacrylate is 1: 2. The emulsifier is a composite emulsifier consisting of sodium dodecyl sulfate and polyethylene glycol octyl phenyl ether (OP-10). The cross-linking agent is a compound cross-linking agent of GMA and allyl phthalate. The dispersant is sodium dihydrogen phosphate. The wetting agent is sodium dodecyl sulfate. The pH regulator is sodium bicarbonate. The initiator is redox initiator, wherein the reducing agent is sodium hydrosulfite, and the oxidizing agent is di-tert-butyl peroxide (DTBP). The inorganic material is magnesium sulfate whisker.
Example 2
A preparation method of a strong core toughening agent for a PVC foam board comprises the following steps:
(1) adding 200 parts by weight of monomer, 150 parts by weight of water, 5 parts by weight of emulsifier, 4 parts by weight of cross-linking agent, 1.6 parts by weight of dispersant, 0.08 part by weight of wetting agent, 3 parts by weight of magnesium sulfate whisker and 0.25 part by weight of pH regulator into a reaction kettle, discharging oxygen by nitrogen, starting stirring, controlling the rotating speed to be 100 plus 200r/min, and heating to 45-50 ℃;
(2) when the temperature of the emulsion is constant at 45-50 ℃, adding 0.5 weight part of initiator in total amount, continuing stirring for reaction, and controlling the reaction time of the emulsion for 5-18 h;
(3) heating to 75 ℃, curing for 1-2h, then cooling to 35 ℃, discharging to obtain copolymer emulsion;
(4) and demulsifying, washing and drying the prepared copolymer emulsion to obtain powdery emulsion particles.
The monomer consists of hydroxypropyl acrylate and lauryl methacrylate, and the mass ratio of the hydroxypropyl acrylate to the lauryl methacrylate is 1: 2. The emulsifier is a composite emulsifier consisting of sodium dodecyl sulfate and polyethylene glycol octyl phenyl ether (OP-10). The cross-linking agent is a compound cross-linking agent of vinyl triethoxysilane and vinyl trimethoxysilane. The dispersant is sodium dihydrogen phosphate. The wetting agent is sodium dodecyl benzene sulfonate. The pH regulator is sodium bicarbonate. The initiator adopts potassium persulfate. The inorganic material is calcium carbonate whisker.
Example 3
A preparation method of a strong core toughening agent for a PVC foam board comprises the following steps:
(1) adding 180 parts by weight of monomer, 130 parts by weight of water, 3.5 parts by weight of emulsifier, 2 parts by weight of cross-linking agent, 1.2 parts by weight of dispersant, 0.04 part by weight of wetting agent, 2.5 parts by weight of magnesium sulfate whisker and 0.15 part by weight of pH regulator into a reaction kettle, discharging oxygen by nitrogen, starting stirring, controlling the rotating speed to be 100 plus 200r/min, and heating to 45-50 ℃;
(2) when the temperature of the emulsion is constant at 45-50 ℃, adding 0.45 weight part of initiator in total amount, continuing stirring for reaction, and controlling the reaction time of the emulsion for 5-18 h;
(3) heating to 75 ℃, curing for 1-2h, then cooling to 35 ℃, discharging to obtain copolymer emulsion;
(4) and demulsifying, washing and drying the prepared copolymer emulsion to obtain powdery emulsion particles.
The monomer consists of hydroxypropyl acrylate and lauryl methacrylate, and the mass ratio of the hydroxypropyl acrylate to the lauryl methacrylate is 1: 2. The emulsifier is a composite emulsifier consisting of sodium dodecyl sulfate and polyethylene glycol octyl phenyl ether (OP-10). The cross-linking agent is a compound cross-linking agent of allyl phthalate and vinyl tri (beta-methoxyethoxy) silane. The dispersant is sodium dihydrogen phosphate. The wetting agent is sodium dodecyl sulfate and sodium dodecyl benzene sulfonate. The pH regulator is sodium bicarbonate. The initiator adopts ammonium persulfate. The inorganic material is glass fiber.
The mechanical property test of the toughening agent and PVC blended material obtained by the invention comprises the following steps:
taking 100 parts of PVC, 10 parts of toughening agent (example 1) and 8 parts of ingredient (other processing aids of PVC) to blend and extrude through a PVC production line, and cutting a section bar 1m, and marking as a sample 1;
taking 100 parts of PVC, 10 parts of toughening agent (example 2) and 8 parts of ingredients (other processing aids of PVC) to blend and extrude through a PVC production line, and cutting a section bar 1m, and marking as a sample 2;
taking 100 parts of PVC, 10 parts of toughening agent (example 3) and 8 parts of ingredients (other processing aids of PVC) to blend and extrude through a PVC production line, and cutting a section bar 1m, and marking as a sample 3;
taking 100 parts of PVC and 8 parts of ingredients (other processing aids of the PVC) to be blended and extruded by a PVC production line, and cutting a section bar 1m, and marking as a sample 4;
100 parts of PVC, 10 parts of a commercial toughening agent (PVC impact modifier ACR401 of Shijiazhuang Hongda Zinc Co., Ltd.) and 8 parts of ingredients (other processing aids of PVC) are blended and extruded by a PVC production line, and then a section bar 1m is cut out and recorded as sample 5.
The above samples 1 to 5 were examined for their notched impact strength and grip performance index (notched Izod impact strength: GB1843-2008, grip strength: GB/T11718.9-1989), and the results are shown in the following table:
from the above experimental results, it can be seen that the core layer strength and nail-holding power of the PVC profile (sample 1-3) obtained by using the toughening agent of the present invention are greatly improved compared to the PVC profile (sample 4) not using the toughening agent and the PVC profile (sample 5) using the common toughening agent on the market.
The foregoing is merely exemplary and illustrative of the present invention and various modifications, additions and substitutions may be made by those skilled in the art to the specific embodiments described without departing from the scope of the present invention as defined in the accompanying claims.
Claims (5)
1. A preparation method of a strong core toughening agent for a PVC foam board is characterized by comprising the following steps:
(1) adding 200 parts by weight of monomer of 150-; the cross-linking agent is any one or more of GMA, allyl phthalate, vinyl triethoxysilane, vinyl trimethoxysilane and vinyl tri (beta-methoxyethoxy) silane; the wetting agent is one or two of sodium dodecyl sulfate and sodium dodecyl benzene sulfonate; the inorganic material is any one of magnesium sulfate whisker, calcium carbonate whisker, glass fiber and calcium sulfate whisker;
(2) when the temperature of the emulsion is constant at 45-50 ℃, adding 0.25-0.5 weight part of initiator in total, cooling to 35-40 ℃, continuing stirring for reaction, and controlling the reaction time of the emulsion for 5-18 h;
(3) heating to 75 ℃, curing for 1-2h, then cooling to 35 ℃, discharging to obtain copolymer emulsion;
(4) and demulsifying, washing and drying the prepared copolymer emulsion to obtain powdery emulsion particles.
2. The method for preparing a strong core toughening agent for PVC foam boards as claimed in claim 1, wherein the emulsifier is a composite emulsifier consisting of sodium dodecyl sulfate and polyethylene glycol octyl phenyl ether (OP-10).
3. The method for preparing a strong core toughening agent for PVC foam boards as claimed in claim 1, wherein the dispersing agent is sodium dihydrogen phosphate.
4. The method for preparing the strong core toughening agent for the PVC foam board according to claim 1, wherein the pH regulator is sodium bicarbonate.
5. The method for preparing a strong core toughening agent for PVC foam boards as claimed in claim 1, wherein the initiator is redox initiator, wherein the reducing agent is sodium dithionite and the oxidizing agent is di-tert-butyl peroxide (DTBP), or the initiator is any one of potassium persulfate and ammonium persulfate.
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Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103890085A (en) * | 2012-04-03 | 2014-06-25 | Lg化学株式会社 | Composition containing cross-linked polymer nanoparticles, method for preparing copolymer using the composition, and vinyl chloride resin having enhanced foam moldability |
| CN107417855A (en) * | 2017-06-14 | 2017-12-01 | 长春工业大学 | A kind of organic inorganic hybridization emulsion particle toughness reinforcing hydrophobic association hydrogel and preparation method thereof |
| CN109897131A (en) * | 2019-03-04 | 2019-06-18 | 浙江华慧塑业有限公司 | A kind of polyvinyl chloride compatilizer and preparation method thereof |
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- 2021-01-29 CN CN202110129324.5A patent/CN112778452B/en active Active
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103890085A (en) * | 2012-04-03 | 2014-06-25 | Lg化学株式会社 | Composition containing cross-linked polymer nanoparticles, method for preparing copolymer using the composition, and vinyl chloride resin having enhanced foam moldability |
| CN107417855A (en) * | 2017-06-14 | 2017-12-01 | 长春工业大学 | A kind of organic inorganic hybridization emulsion particle toughness reinforcing hydrophobic association hydrogel and preparation method thereof |
| CN109897131A (en) * | 2019-03-04 | 2019-06-18 | 浙江华慧塑业有限公司 | A kind of polyvinyl chloride compatilizer and preparation method thereof |
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Denomination of invention: A kind of preparation method of strong core toughening agent for PVC foam board Effective date of registration: 20220729 Granted publication date: 20220426 Pledgee: Rizhao Bank Co.,Ltd. Weifang Gaomi sub branch Pledgor: Shandong Yuanbang New Material Co.,Ltd. Registration number: Y2022370010122 |
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Address after: 261500 west of Xuxin road and south of Fuhe Road, Renhe Industrial Park, Jiangzhuang Town, Gaomi City, Weifang City, Shandong Province Patentee after: Shandong Yuanbang New Material Co.,Ltd. Address before: 261500 west of Xuxin road and south of Fuhe Road, Renhe Industrial Park, Jiangzhuang Town, Gaomi City, Weifang City, Shandong Province Patentee before: Shandong Yuanbang New Material Co.,Ltd. |