CN107501461B - Special copolymerization type PVC (polyvinyl chloride) auxiliary agent with heat stabilizer and plasticizing functions - Google Patents
Special copolymerization type PVC (polyvinyl chloride) auxiliary agent with heat stabilizer and plasticizing functions Download PDFInfo
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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
- C08F218/00—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 an acyloxy radical of a saturated carboxylic acid, of carbonic acid or of a haloformic acid
- C08F218/02—Esters of monocarboxylic acids
- C08F218/04—Vinyl esters
- C08F218/10—Vinyl esters of monocarboxylic acids containing three or more carbon atoms
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- 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
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- 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
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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
- C08F220/1808—C8-(meth)acrylate, e.g. isooctyl (meth)acrylate or 2-ethylhexyl (meth)acrylate
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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
- C08L2201/00—Properties
- C08L2201/08—Stabilised against heat, light or radiation or oxydation
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Abstract
The invention provides a copolymer type PVC special aid with heat stabilizer and plasticizing functions, which has the structural formula as follows:
the material is obtained by free radical polymerization of the following three vinyl monomers:
Description
Technical Field
The invention relates to a copolymer type PVC special aid with double functions of a heat stabilizer and plasticization, belonging to the field of chemical synthesis.
Background
As a common plastic, PVC is widely used in production and life, and most of these PVC products are obtained by thermal processing of PVC resin. The structure of PVC determines its instability during processing, and plasticizers and heat stabilizers must be added. Plasticizers and heat stabilizers which are widely used today are various, but most are small molecules with single functions. This results in complexity in the PVC processing, and these small molecule aids have poor compatibility with the PVC macromolecular chains and tend to migrate out during use of the PVC. Once migrated out, these small molecule aids not only change the properties of PVC, but also may directly harm people's health. Therefore, there is a need to develop a multifunctional non-migrating PVC processing aid.
Disclosure of Invention
The invention aims to solve the technical problems of single function, poor compatibility with PVC and easy migration of the existing PVC processing aid. Provides a PVC special-purpose auxiliary agent which is copolymerized by several functional monomers and has the functions of heat stabilizer and plasticizing and does not migrate.
In order to solve the problems, the technical scheme of the invention is as follows:
a copolymer PVC special-purpose auxiliary agent with heat stabilizer and plasticizing double functions has the following structure:
the material is obtained by free radical polymerization of the following three vinyl monomers:
wherein R1 is a C1 to C10 hydrocarbyl group, with an average of 0 to 3 branches per hydrocarbyl group; r2 is a methyl group or a hydrogen atom, R3 is a C1 to C17 hydrocarbon group containing an average of 0 to 3 epoxy groups per hydrocarbon group; mn+Is n-valent metal ions, and M is one of lithium, calcium, zinc, barium, bismuth, iron, cobalt and nickel; r4 is a C1 to C17 hydrocarbon group containing an average of 0 to 3 epoxy groups per hydrocarbon group, R5 is a methyl group or a hydrogen atom; x is between 1 and 10, y is between 1 and 5, z is between 1 and 10, and 5 ≦ x + y + z ≦ 25.
The monomer A can be: methyl acrylate, methyl methacrylate, ethyl acrylate, ethyl methacrylate, n-propyl acrylate, n-propyl methacrylate, isopropyl acrylate, isopropyl methacrylate, glycidyl acrylate, glycidyl methacrylate, n-butyl acrylate, n-butyl methacrylate, isobutyl acrylate, isobutyl methacrylate, tert-butyl acrylate, tert-butyl methacrylate, n-pentyl acrylate, n-pentyl methacrylate, isopentyl acrylate, isopentyl methacrylate, neopentyl acrylate, neopentyl methacrylate, tert-hexyl acrylate, tert-hexyl methacrylate, n-hexyl acrylate, n-hexyl methacrylate, isohexyl acrylate, isohexyl methacrylate, neohexyl acrylate, neohexyl methacrylate, tert-hexyl acrylate, tert-hexyl methacrylate, n-heptyl acrylate, n-hexyl methacrylate, isopropyl acrylate, isohexyl methacrylate, n-heptyl acrylate, n-hexyl methacrylate, n-heptyl acrylate, n-hexyl methacrylate, n-pentyl methacrylate, n, N-heptyl methacrylate, isoheptyl acrylate, isoheptyl methacrylate, neoheptyl acrylate, neoheptyl methacrylate, tert-heptyl acrylate, tert-heptyl methacrylate, n-octyl acrylate, n-octyl methacrylate, isooctyl acrylate, isooctyl methacrylate, neooctyl acrylate, neooctyl methacrylate, tert-octyl acrylate, tert-octyl methacrylate, n-nonyl acrylate, one or more of n-nonyl methacrylate, isononyl acrylate, isononyl methacrylate, neononyl acrylate, neononyl methacrylate, tert-nonyl acrylate, tert-nonyl methacrylate, n-decyl acrylate, n-decyl methacrylate, isodecyl acrylate, isodecyl methacrylate, neodecyl acrylate, neodecyl methacrylate, tert-decyl acrylate, tert-decyl methacrylate and the like. Inexpensive bulk chemicals such as methyl acrylate, methyl methacrylate, glycidyl acrylate, glycidyl methacrylate, isooctyl acrylate, isooctyl methacrylate, and the like, which are directly commercially available, are preferred.
The monomer B can be: lithium acrylate, lithium methacrylate, zinc acetate acrylate, zinc acetate methacrylate, calcium diacrylate, calcium dimethacrylate, zinc diacrylate, zinc dimethacrylate, zinc propionate acrylate, zinc propionate methacrylate, zinc epoxy propionate acrylate, zinc epoxy propionate methacrylate, zinc butyrate acrylate, zinc butyrate methacrylate, zinc butyrate acrylate, zinc epoxy butyrate methacrylate, zinc valerate acrylate, zinc valerate methacrylate, zinc caproate acrylate, zinc caproate methacrylate, zinc heptacrylate, zinc caprylate acrylate, zinc caprylate methacrylate, zinc isooctanoate acrylate, zinc isooctanoate methacrylate, zinc nonanoate acrylate, zinc nonanoate methacrylate, zinc decanoate acrylate, zinc decanoate methacrylate, zinc laurate acrylate, zinc laurate methacrylate, zinc lactate, zinc methacrylate, zinc acetate, zinc acrylate, zinc acetate, zinc acrylate, zinc methacrylate, zinc acetate, zinc acrylate, zinc methacrylate, zinc acrylate, one or more of acrylic acid zinc oleate, methacrylic acid zinc oleate, acrylic acid epoxy zinc oleate, methacrylic acid epoxy zinc oleate, acrylic acid zinc linolenate, methacrylic acid zinc linolenate and the like. (for convenience, calcium in the metal carboxylate can be replaced by barium, and zinc can be replaced by iron/cobalt/nickel/bismuth, which are not listed here.) cheap bulk chemicals which can be purchased directly from the market are preferred, or monomers which are easy to synthesize and have easily available synthetic raw materials, such as calcium diacrylate, calcium dimethacrylate, zinc diacrylate, zinc dimethacrylate, zinc laurate acrylate, zinc laurate methacrylate, and the like.
The monomer C can be: one or more of vinyl acetate, vinyl propionate, vinyl epoxypropionate, vinyl propionate, vinyl acrylate, vinyl methacrylate, vinyl butyrate, vinyl valerate, vinyl caproate, vinyl heptanoate, vinyl caprylate, vinyl pelargonate, vinyl caprate, vinyl laurate, vinyl oleate, vinyl stearate, vinyl epoxyoleate, vinyl linoleate, vinyl epoxylinoleate and the like. Inexpensive commodity chemicals such as vinyl acetate, vinyl propionate, vinyl laurate, which are directly commercially available, are preferred.
The preparation method of the copolymerization type PVC special auxiliary agent with the heat stabilizer and the plasticizing dual functions comprises the following steps:
(1) preparation of functional monomer A:
the functional monomer A can be methyl acrylate or methyl methacrylate directly used for copolymerization, and acrylic ester or methacrylic ester used for copolymerization corresponding to alcohol can be obtained by rectifying and extracting after ester exchange reaction of methyl acrylate or methyl methacrylate and various alcohols.
(2) Preparation of functional monomer B:
① dissolving equal molar amount of sodium hydroxide solid with acrylic acid or methacrylic acid in water to obtain sodium acrylate or sodium methacrylate solution, dissolving equal molar amount of zinc/bismuth/iron/cobalt/nickel metal chloride and sodium hydroxide in water to obtain equal volume of water solution, slowly adding the water solution of zinc/bismuth/iron/cobalt/nickel metal chloride and sodium hydroxide into the vigorously stirred sodium acrylate or sodium methacrylate solution at the same time, stopping stirring to obtain basic zinc acrylate/bismuth/iron/cobalt/nickel or basic zinc methacrylate/bismuth/iron/cobalt/nickel suspension, repeatedly washing and vacuum-filtering the suspension until no significant sodium chloride remains to obtain aqueous basic zinc acrylate/bismuth/iron/cobalt/nickel or basic zinc methacrylate/bismuth/iron/cobalt/nickel suspension, drying at room temperature to obtain dry basic zinc acrylate/bismuth/iron/cobalt/nickel or basic zinc methacrylate/bismuth/iron/cobalt/nickel or basic zinc methacrylate/cobalt/nickel solid, and optionally adding the aqueous solution of calcium carbonate/bismuth/iron/cobalt/nickel or calcium carbonate to the corresponding sodium acrylate or calcium carbonate or barium methacrylate or cobalt/nickel carbonate solution, and sodium carbonate or barium carbonate, and sodium carbonate/cobalt carbonate/carbonate solution, and sodium carbonate/carbonate can be used for further reacted with twice molar amount of calcium carbonate or barium carbonate, and sodium carbonate, and lithium carbonate.
(3) Radical copolymerization of three types of functional monomers:
AIBN is used as an initiator, toluene-methanol (volume ratio is 3: 1-5: 1) is used as a solvent, and the temperature is controlled to be 60-90 ℃. The mass ratio of the total monomers to the solvent is controlled to be 1:2 to 1: 10. The molar ratio of the monomer A, B is controlled to be 1:1 to 5:1, the molar ratio of the monomer C, B is controlled to be 1:1 to 5:1, and the molar ratio of the monomer A, C is controlled to be 5:1 to 1: 5. Controlling the mass ratio of the total monomers to the initiator AIBN between 5:1 and 20: 1. the radical polymerization was carried out under the above conditions for 10 minutes to 2 hours, then rapidly cooled to room temperature, and filtered to obtain a small block copolymer. The copolymer is crushed, repeatedly washed by a mixed solvent of toluene and methanol (the volume ratio is 3:1 to 5:1), and dried in vacuum at 10 ℃ to 30 ℃ for 1 to 5 hours to obtain a pure copolymer without unreacted monomers and solvents. Esters, isooctyl methacrylate, and the like.
Detailed description of the invention
The present invention will be described in detail below, and various changes and modifications can be made by workers in the field without departing from the technical spirit of the present invention. The technical scope of the present invention is not limited to the content of the specification, and must be determined according to the scope of the claims.
Example 1
5mL of acrylic acid and 25mL of water are mixed in a 250mL three-mouth round bottle, 2.90g of sodium hydroxide solid is added to the mixture, and the mixture is stirred for ice-water bath to react fully, so that sodium acrylate aqueous solution is obtained. The corresponding aqueous solutions were prepared by dissolving 9.87g of zinc chloride and 2.90g of sodium hydroxide in 60mL of water, respectively. And (3) slowly dripping the zinc chloride aqueous solution and the sodium hydroxide aqueous solution (0.5mL/min) into the sodium acrylate solution which is stirred vigorously (1000r/min) at the same time, and reacting at room temperature. And stopping stirring a moment after the zinc chloride aqueous solution and the sodium hydroxide aqueous solution are dripped, so as to obtain a white basic zinc acrylate suspension with the pH value of about 7. And repeatedly washing and filtering the suspension until no obvious sodium chloride residue exists, and obtaining the aqueous basic zinc acrylate solid. Drying at room temperature to obtain dry basic zinc acrylate white solid.
2.10g of calcium dimethacrylate, 0.77g of zinc basic acrylate and 3.10g of vinyl stearate were simultaneously charged into a 100mL three-necked round flask containing 50mL of a toluene-methanol (volume ratio: 4:1) mixed solvent, and stirred at room temperature of 200r/min until the monomers were dissolved. 0.77g of AIBN was dissolved in the above round bottle. Heating to 80 ℃ for reflux, stirring, reacting for 1 hour, adding 10mL of toluene-methanol (volume ratio 4:1) mixed solvent dissolved with 0.38g of AIBN, and continuing to react for 0.5 hour. A white to yellowish block copolymer was obtained. After the copolymer was broken, the copolymer was repeatedly washed with a mixed solvent of toluene and methanol (volume ratio: 4:1), and then dried under vacuum at 25 ℃ for 12 hours to obtain a pure copolymer (referred to as copolymer A) containing no unreacted monomer and no solvent. The copolymer can be directly used for thermal processing of PVC resin.
PVC with different formulas is mixed for 5min at a high speed, then is mixed for 5min on a double-roll open mill under the plastication conditions that the rotating speed of a front roll is 18r/min, the rotating speed of a rear roll is 20r/min, the roll temperature is 170 ℃, and sheets are discharged after complete plastication. And comparing the synthesized copolymer PVC auxiliary agent by taking a commercially available composite calcium-zinc heat stabilizer S-501 as a reference. And carrying out thermal stability test on the obtained PVC sheet according to a GB/T2917.1-2002 polyvinyl chloride thermal stability test method-Congo red method. The formulations and thermal stability test results are given in the following table:
example 2
1.84g of isooctyl acrylate, 0.77g of zinc basic acrylate and 1.00g of vinyl propionate were simultaneously placed in a 100mL three-necked round flask containing 50mL of a toluene-methanol (volume ratio: 4:1) mixed solvent, and stirred at 200r/min at room temperature until the monomers were dissolved. 0.72g of AIBN was dissolved in the above round flask. Heating to 80 ℃ for reflux, stirring, reacting for 1 hour, adding 10mL of toluene-methanol (volume ratio 4:1) mixed solvent dissolved with 0.36g of AIBN, and continuing to react for 0.5 hour. A white to yellowish block copolymer was obtained. The copolymer was crushed, washed repeatedly with a mixed solvent of toluene and methanol (volume ratio 4:1), and dried under vacuum at 25 ℃ for 12 hours to obtain a pure copolymer (designated as copolymer B) containing no unreacted monomer and no solvent. The copolymer can be directly used for thermal processing of PVC resin.
PVC with different formulas is mixed for 5min at a high speed, then is mixed for 5min on a double-roll open mill under the plastication conditions that the rotating speed of a front roll is 18r/min, the rotating speed of a rear roll is 20r/min, the roll temperature is 170 ℃, and sheets are discharged after complete plastication. And comparing the synthesized copolymer PVC auxiliary agent by taking a commercially available composite calcium-zinc heat stabilizer S-501 as a reference. And carrying out thermal stability test on the obtained PVC sheet according to a GB/T2917.1-2002 polyvinyl chloride thermal stability test method-Congo red method. The formulations and thermal stability test results are given in the following table:
example 3
1.53g of basic zinc acrylate was dissolved in a 100mL three-necked round flask containing 25mL of a toluene-methanol (volume ratio: 5:1) mixed solvent, and the mixture was refluxed at room temperature and stirred (200 r/min). 25mL of a toluene-methanol (volume ratio 5:1) mixed solvent in which 1.44g of isooctanoic acid was dissolved was added dropwise (1 mL/min). After the addition, the reaction was continued at room temperature for 1 hour. A toluene-methanol (volume ratio 5:1) solution of zinc isooctanoate acrylate containing a very small amount of unreacted basic zinc acrylate and isooctanoate was obtained.
2.26g of vinyl laurate, 1.42g of glycidyl methacrylate and 1.29g of AIBN were added to the above solution, and the mixture was stirred under reflux at room temperature (200r/min), mixed uniformly, and then heated to 65 ℃ to start polymerization. After 1.5 hours of the reaction, 10mL of a toluene-methanol mixed solvent (volume ratio: 5:1) in which 0.65g of AIBN was dissolved was added, and the reaction was continued for 0.5 hour. A white to yellowish block copolymer was obtained. The copolymer was crushed, washed repeatedly with a mixed solvent of toluene and methanol (volume ratio 5:1), and dried under vacuum at 25 ℃ for 12 hours to obtain a pure copolymer (designated as copolymer C) containing no unreacted monomer and no solvent. The copolymer can be directly used for thermal processing of PVC resin.
PVC with different formulas is mixed for 5min at a high speed, then is mixed for 5min on a double-roll open mill under the plastication conditions that the rotating speed of a front roll is 18r/min, the rotating speed of a rear roll is 20r/min, the roll temperature is 170 ℃, and sheets are discharged after complete plastication. And comparing the synthesized copolymer PVC auxiliary agent by taking a commercially available composite calcium-zinc heat stabilizer S-501 as a reference. And carrying out thermal stability test on the obtained PVC sheet according to a GB/T2917.1-2002 polyvinyl chloride thermal stability test method-Congo red method. The formulations and thermal stability test results are given in the following table:
Claims (7)
1. a copolymerization type PVC special auxiliary agent has the following structure:
wherein R is1Is a C1 to C10 hydrocarbyl group containing an average of 0 to 3 branches per hydrocarbyl group; r2Is a methyl group or a hydrogen atom, R3Is a C1 to C17 hydrocarbon group containing an average of 0 to 3 epoxy groups per hydrocarbon group; mn+Is n-valent metal ion, and M is selected from lithium, calcium, zinc, barium, bismuth, iron, cobalt, and nickelOne kind of the material is selected; r4Is a hydrocarbon radical of C1 to C17 containing an average of 0 to 3 epoxy groups per hydrocarbon radical, R5Is methyl or a hydrogen atom; x is between 1 and 10, y is between 1 and 5, z is between 1 and 10, and 5 ≦ x + y + z ≦ 25, the polymer being obtained by free radical polymerization of the following three types of vinyl monomers:
2. the adjuvant according to claim 1, characterized in that: the monomer A is as follows: methyl acrylate, methyl methacrylate, ethyl acrylate, ethyl methacrylate, n-propyl acrylate, n-propyl methacrylate, isopropyl acrylate, isopropyl methacrylate, glycidyl acrylate, glycidyl methacrylate, n-butyl acrylate, n-butyl methacrylate, isobutyl acrylate, isobutyl methacrylate, tert-butyl acrylate, tert-butyl methacrylate, n-pentyl acrylate, n-pentyl methacrylate, isopentyl acrylate, isopentyl methacrylate, neopentyl acrylate, neopentyl methacrylate, tert-hexyl acrylate, tert-hexyl methacrylate, n-hexyl acrylate, n-hexyl methacrylate, isohexyl acrylate, isohexyl methacrylate, neohexyl acrylate, neohexyl methacrylate, tert-hexyl acrylate, tert-hexyl methacrylate, n-heptyl acrylate, n-hexyl methacrylate, isopropyl acrylate, isohexyl methacrylate, n-heptyl acrylate, n-hexyl methacrylate, n-heptyl acrylate, n-hexyl methacrylate, n-pentyl methacrylate, n, N-heptyl methacrylate, isoheptyl acrylate, isoheptyl methacrylate, neoheptyl acrylate, neoheptyl methacrylate, tert-heptyl acrylate, tert-heptyl methacrylate, n-octyl acrylate, n-octyl methacrylate, isooctyl acrylate, isooctyl methacrylate, neooctyl acrylate, neooctyl methacrylate, tert-octyl acrylate, tert-octyl methacrylate, n-nonyl acrylate, n-nonyl methacrylate, isononyl acrylate, isononyl methacrylate, neononyl acrylate, neononyl methacrylate, tert-nonyl acrylate, tert-nonyl methacrylate, n-decyl acrylate, n-decyl methacrylate, isodecyl acrylate, isodecyl methacrylate, neodecyl acrylate, neodecyl methacrylate, tert-decyl acrylate, tert-decyl methacrylate.
3. The adjuvant according to claim 1, characterized in that: the monomer B is as follows: lithium acrylate, lithium methacrylate, zinc acetate acrylate, zinc acetate methacrylate, calcium diacrylate, calcium dimethacrylate, zinc diacrylate, zinc dimethacrylate, zinc propionate acrylate, zinc propionate methacrylate, zinc epoxy propionate acrylate, zinc epoxy propionate methacrylate, zinc butyrate acrylate, zinc butyrate methacrylate, zinc butyrate acrylate, zinc epoxy butyrate methacrylate, zinc valerate acrylate, zinc valerate methacrylate, zinc caproate acrylate, zinc caproate methacrylate, zinc heptacrylate, zinc caprylate acrylate, zinc caprylate methacrylate, zinc isooctanoate acrylate, zinc isooctanoate methacrylate, zinc nonanoate acrylate, zinc nonanoate methacrylate, zinc decanoate acrylate, zinc decanoate methacrylate, zinc laurate acrylate, zinc laurate methacrylate, zinc lactate, zinc methacrylate, zinc acetate, zinc acrylate, zinc acetate, zinc acrylate, zinc methacrylate, zinc acetate, zinc acrylate, zinc methacrylate, zinc acrylate, one or more of acrylic acid zinc oleate, methacrylic acid zinc oleate, acrylic acid epoxy zinc oleate, methacrylic acid epoxy zinc oleate, acrylic acid zinc linolenate, methacrylic acid zinc linolenate, acrylic acid epoxy zinc linolenate, and methacrylic acid zinc linolenate.
4. The adjuvant according to claim 1, characterized in that: the preparation method of the monomer B with M being zinc, bismuth, iron, cobalt and nickel comprises the following steps: fully reacting equimolar sodium hydroxide solid with acrylic acid or methacrylic acid in an aqueous solution to obtain a sodium acrylate or sodium methacrylate solution; respectively dissolving zinc/bismuth/iron/cobalt/nickel metal chloride and sodium hydroxide with equal molar weight in water to prepare an aqueous solution with equal volume; slowly dripping the zinc/bismuth/iron/cobalt/nickel metal chloride aqueous solution and the sodium hydroxide aqueous solution into the vigorously stirred sodium acrylate or sodium methacrylate solution at the same speed, stopping stirring after the dripping of the zinc/bismuth/iron/cobalt/nickel metal chloride aqueous solution and the sodium hydroxide aqueous solution is finished, and obtaining basic zinc acrylate/bismuth/iron/cobalt/nickel or basic zinc methacrylate/bismuth/iron/cobalt/nickel suspension; and repeatedly washing and filtering the suspension until no obvious sodium chloride residue is left to obtain a hydrous zinc/bismuth/iron/cobalt/nickel subacrylate or zinc/bismuth/iron/cobalt/nickel subacrylate solid, drying at room temperature to obtain a dried zinc/bismuth/iron/cobalt/nickel subacrylate or zinc/bismuth/iron/cobalt/nickel subacrylate solid, dissolving the solid in a toluene-methanol mixed solvent, and directly copolymerizing or further reacting with various carboxylic acids to obtain the corresponding zinc/bismuth/iron/cobalt/nickel acrylate carboxylate or zinc/bismuth/iron/cobalt/nickel methacrylate carboxylate.
5. The adjuvant according to claim 1, characterized in that: the preparation method of the monomer B with M being lithium, calcium and barium comprises the following steps: fully reacting equimolar sodium hydroxide solid with acrylic acid or methacrylic acid in an aqueous solution to obtain a sodium acrylate or sodium methacrylate solution; adding a lithium/calcium/barium metal chloride aqueous solution into the sodium acrylate or sodium methacrylate solution with corresponding molar weight, stirring at room temperature and evaporating the solvent to obtain a lithium/calcium/barium acrylate or lithium/calcium/barium methacrylate carboxylate and lithium/calcium/barium metal chloride mixture; repeated recrystallization is carried out to extract the low-solubility lithium acrylate/calcium/barium or lithium methacrylate/calcium/barium carboxylate, and the carboxylate is dissolved in a toluene-methanol mixed solvent and directly used for copolymerization.
6. The adjuvant according to claim 1, characterized in that: the monomer C is as follows: vinyl acetate, vinyl propionate, vinyl epoxy propionate, vinyl acrylate, vinyl methacrylate, vinyl butyrate, vinyl valerate, vinyl caproate, vinyl heptanoate, vinyl caprylate, vinyl pelargonate, vinyl caprate, vinyl laurate, vinyl oleate, vinyl stearate, vinyl epoxy oleate, vinyl linoleate, vinyl epoxy linoleate and the like, or a combination of more of the vinyl acetate, the vinyl propionate, the vinyl epoxy propionate, the vinyl acrylate, the vinyl methacrylate, the vinyl butyrate, the vinyl valerate, the vinyl heptanoate, the vinyl caprylate, the vinyl pel.
7. The process for the preparation of the adjuvant according to claim 1, characterized in that: using AIBN as an initiator, using toluene-methanol with a volume ratio of 3:1 to 5:1 as a solvent, controlling the temperature to be 60-90 ℃, controlling the mass ratio of the total monomer to the solvent to be 1: 2-1: 10, controlling the molar ratio of the monomer A, B to be 1: 1-5: 1, controlling the molar ratio of the monomer C, B to be 1: 1-5: 1, controlling the molar ratio of the monomer A, C to be 5: 1-1: 5, controlling the mass ratio of the total monomer to the initiator AIBN to be 5: 1-20: 1, carrying out free radical polymerization reaction for 10 minutes to 2 hours under the conditions, then rapidly cooling to room temperature, filtering to obtain a small block copolymer, crushing the copolymer, repeatedly washing the copolymer by using a toluene-methanol mixed solvent with a volume ratio of 3:1 to 5:1, and then drying the copolymer in vacuum at 10 ℃ to 30 ℃ for 1 to 5 hours to obtain a pure copolymer without unreacted monomers and solvents.
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| CN111138671B (en) * | 2018-11-02 | 2021-09-14 | 四川大学 | Metal-organic high molecular compound and preparation method thereof |
| CN114907512A (en) * | 2022-06-27 | 2022-08-16 | 杭州科思博睿科技有限公司 | Multifunctional additive, preparation method thereof and application thereof in preparation of chlorine-containing polymer material |
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