CN108484813A - A kind of vinyl chloride high polymer and preparation method thereof - Google Patents
A kind of vinyl chloride high polymer and preparation method thereof Download PDFInfo
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- CN108484813A CN108484813A CN201810135565.9A CN201810135565A CN108484813A CN 108484813 A CN108484813 A CN 108484813A CN 201810135565 A CN201810135565 A CN 201810135565A CN 108484813 A CN108484813 A CN 108484813A
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- 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
- C08F214/00—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 a halogen
- C08F214/02—Monomers containing chlorine
- C08F214/04—Monomers containing two carbon atoms
- C08F214/06—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
- C08F2/00—Processes of polymerisation
- C08F2/12—Polymerisation in non-solvents
- C08F2/16—Aqueous medium
- C08F2/20—Aqueous medium with the aid of macromolecular dispersing agents
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- Chemical Kinetics & Catalysis (AREA)
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- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Graft Or Block Polymers (AREA)
Abstract
The present invention relates to a kind of vinyl chloride high polymers and preparation method thereof.Specifically, it is emulsion polyvinyl chloride resin used and preparation method thereof in artificial leather preparation process.The vinyl chloride high polymer be with the raw materials such as vinyl chloride, acrylic ester monomer, vinylacetate, molecular weight regulator, initiator, dispersant and deionized water, through mixing, reaction, washing, dehydration, drying and screening and etc. and be made.Vinyl chloride high polymer prepared by method using the present invention, raw materials used cheap, production cost is low.The polrvinyl chloride product made of this vinyl chloride high polymer, shock resistance are good.
Description
Technical field
The present invention relates to a kind of resins and preparation method thereof.Specifically, it is lotion used in artificial leather preparation process ----
Corvic and preparation method thereof.
Background technology
It is both known about in chemical industry, as the polrvinyl chloride product of artificial leather etc is mostly by fabric and to be compounded in fabric table
Face lotion drying after formed surface layer and constitute.Lotion therein is polyvinyl chloride.And vinyl chloride mobility is poor, therefore
It needs that modifier is added in process of production to promote its plasticizing, it is comprehensive with the appearance for improving its mobile performance and artificial leather product
Close performance.In addition, being formed in the surface layer of fabric surface with polyvinyl chloride has the characteristics that black brittleness, shock resistance are poor.Cause
In process of production, and anti-impact modifier need to be added to improve its shock resistance in this.Wherein, the processing of polyvinyl-chloride use changes
Property agent be esters of acrylic acid(ACR), anti-impact modifier is haloflex(CPE), methyl methacrylate-butadiene-benzene
Ethylene(MBS)And esters of acrylic acid(ACR).And above-mentioned esters of acrylic acid(ACR), haloflex(CPE)And methacrylic acid
Methyl esters-butadiene-styrene(MBS)It is expensive so that the production cost of polrvinyl chloride product is higher.
Invention content
The problem to be solved in the present invention is to provide a kind of vinyl chloride high polymer.This vinyl chloride high polymer, raw materials used valence
Lattice are cheap, and production cost is low.The polrvinyl chloride product made of this vinyl chloride high polymer, shock resistance are good.
The invention solves another problem be to provide a kind of method preparing vinyl chloride high polymer.
The invention solves the above problem realized by following scheme:
The vinyl chloride high polymer feature of the present invention is made of following raw material:
45 ~ 65 parts by weight of vinyl chloride;
5 ~ 25 parts by weight of acrylic ester monomer;
5 ~ 15 parts by weight of vinylacetate;
0.01 ~ 0.5 parts by weight of molecular weight regulator;
0.2 ~ 1.2 parts by weight of initiator;
2 ~ 10 parts by weight of dispersant;
90 ~ 120 parts by weight of deionized water.
Wherein:
The acrylics monomer is ethyl acrylate, butyl acrylate, Isooctyl acrylate monomer and ethyl methacrylate
Two or more mixtures;
The acrylics monomer is with ethyl acrylate, butyl acrylate and methyl methacrylate and according to acrylic acid second
Ester:Butyl acrylate:Methyl methacrylate=1: 3: 1:2 weight ratio mixes;
The molecular weight regulator is to use diallyl maleate, diallyl phthalate and butanediol diacrylate simultaneously
According to diallyl maleate:Diallyl phthalate:Butanediol diacrylate=2:2:1 weight ratio mixing and
At;
The initiator is to use dicetyl peroxydicarbonate(2- ethyls)Ethyl ester and cumyl peroxyneodecanoate and according to peroxidating
Two carbonic acid(2- ethyls)Ethyl ester:Cumyl peroxyneodecanoate=2:1 weight ratio mixes;
The dispersant is with polyvinyl alcohol and polyvinylpyrrolidone methylcellulose graft copolymer and according to polyethylene
Alcohol:Polyvinylpyrrolidone methylcellulose graft copolymer=1:3 weight ratio mixes;;
The method for preparing the vinyl chloride high polymer includes the following steps successively:
First molecular weight regulator, initiator, dispersant and deionized water are added in reaction kettle, while agitating, to reaction
Kettle is vacuumized, and dispersant is made fully to dissolve;
While continuing stirring, vinylacetate is added;Later, the 1/2-2/3 of vinyl chloride is added, and continues to stir 20-30
Minute, keep starting material pre-dispersed;
Later, reaction kettle is heated, so that the material in reaction kettle is warming up to 40-60 degrees Celsius and is reacted;Work as reaction kettle
It is continuous in 2.9 ~ 3.1 hours, be homogeneously added into acrylic ester monomer and remaining chloroethene when interior pressure reduction 0.2MPa
Alkene;
When the pressure in reaction kettle is down to 0.25MPa or less, the temperature of charge in reaction kettle is risen to 70-75 degrees Celsius, and
Keep the temperature 1-2 hours at this temperature;
Later, the material in reaction kettle is poured out and is dehydrated;
Later, to being washed through dewatered material;
Later, second dehydration is carried out to the material after washed;
Later, with 40-50 DEG C of hot wind to being dried into the material through second dehydration;
Finally, the material after drying is sieved with the sieve of 40 mesh, vinyl chloride high polymer is made.
As can be seen from the above scheme, due to primary raw material vinyl chloride, vinylacetate and the acrylic acid of the invention used
Esters monomer is cheap, thus greatly reduces the production cost of polrvinyl chloride product.And the good, anti-impact with processing performance
Hit the excellent feature of performance.In addition, also have the characteristics that it is fire-retardant, insulation, it is corrosion resistant, have wide range of applications.In addition, as a result of
Suspension polymerisation, and the advantages of combine in synthesis nucleocapsid and reticular structure, overcome the chlorine of other synthesis modes preparation
Ethylene copolymer technical maturity is low, auxiliary agent, emulsifier residual is more, product purity is not high, processing performance is bad, impact resistance
Disadvantage that can not be strong.
Specific implementation mode
Invention is further described in detail with reference to embodiments:
Embodiment one
First choose the vinyl chloride of 45 parts by weight, the acrylic ester monomer of 25 parts by weight, the vinylacetate of 15 parts by weight, 0.01
The deionized water of the molecular weight regulator of parts by weight, the initiator of 0.2 parts by weight, the dispersant of 2 parts by weight and 110 parts by weight.
Wherein:
Acrylic ester monomer is ethyl acrylate, butyl acrylate, Isooctyl acrylate monomer, methyl methacrylate and according to third
Olefin(e) acid ethyl ester:Butyl acrylate:Isooctyl acrylate monomer:Methyl methacrylate=1: 3: 1:2 weight ratio mixes;
The molecular weight regulator is to use diallyl maleate, diallyl phthalate, butanediol diacrylate simultaneously
According to diallyl maleate:Diallyl phthalate:Butanediol diacrylate=2: 2:1 weight ratio mixing
It forms;
The initiator is to use dicetyl peroxydicarbonate(2- ethyls)Ethyl ester and cumyl peroxyneodecanoate and according to peroxidating
Two carbonic acid(2- ethyls)Ethyl ester:Cumyl peroxyneodecanoate=2:1 weight ratio mixes.
The dispersant is with polyvinyl alcohol and polyvinylpyrrolidone methylcellulose graft copolymer and according to poly-
Vinyl alcohol:Polyvinylpyrrolidone methylcellulose graft copolymer=1:3 weight ratio mixes.
Then, molecular weight regulator, initiator, dispersant and deionized water are added in reaction kettle, while agitating,
Reaction kettle is vacuumized, dispersant is made fully to dissolve;
While continuing stirring, vinylacetate is added;Later, it is added the 1/2 of vinyl chloride, and continues stirring 20 minutes, is made
Starting material is pre-dispersed;
Later, reaction kettle is heated, so that the material in reaction kettle is warming up to 40 degrees Celsius and is reacted.When in reaction kettle
It is continuous in 2.9 hours, be homogeneously added into acrylic ester monomer and remaining vinyl chloride when pressure reduction 0.2MPa, continue
Reaction:
When the pressure in reaction kettle is down to 0.25MPa or less, the temperature of charge in reaction kettle is risen to 70 degrees Celsius, and herein
At a temperature of keep the temperature 1 hour;
Later, the material in reaction kettle is poured out, centrifugal drier is used in combination to be dehydrated;
Later, to being washed through dewatered material;
Later, second dehydration is carried out to the material after washed with centrifugal drier;
Later, with 40 degrees Celsius of hot wind to being dried into the material through second dehydration;
Finally, the material after drying is sieved with the sieve of 40 mesh, vinyl chloride high polymer is made.
Embodiment two
First choose the vinyl chloride of 55 parts by weight, the acrylic ester monomer of 5 parts by weight, the vinylacetate of 10 parts by weight, 0.05
The deionized water of the molecular weight regulator of parts by weight, the initiator of 0.4 parts by weight, the dispersant of 6 parts by weight and 120 parts by weight.
Wherein:
Acrylic ester monomer is ethyl acrylate, butyl acrylate, Isooctyl acrylate monomer, methyl methacrylate and according to third
Olefin(e) acid ethyl ester:Butyl acrylate:Isooctyl acrylate monomer:Methyl methacrylate=1: 3: 1:2 weight ratio mixes;
The molecular weight regulator is to use diallyl maleate, diallyl phthalate, butanediol diacrylate simultaneously
According to diallyl maleate:Diallyl phthalate:Butanediol diacrylate=2: 2:1 weight ratio mixing
It forms;
The initiator is to use dicetyl peroxydicarbonate(2- ethyls)Ethyl ester and cumyl peroxyneodecanoate and according to peroxidating
Two carbonic acid(2- ethyls)Ethyl ester:Cumyl peroxyneodecanoate=2:1 weight ratio mixes.
The dispersant is with polyvinyl alcohol and polyvinylpyrrolidone methylcellulose graft copolymer and according to poly-
Vinyl alcohol:Polyvinylpyrrolidone methylcellulose graft copolymer=1:3 weight ratio mixes.
Then, molecular weight regulator, initiator, dispersant and deionized water are added in reaction kettle, while agitating,
Reaction kettle is vacuumized, dispersant is made fully to dissolve;
While continuing stirring, vinylacetate is added;Later, it is added the 2/3 of vinyl chloride, and continues stirring 25 minutes, is made
Starting material is pre-dispersed;
Later, reaction kettle is heated, so that the material in reaction kettle is warming up to 45 degrees Celsius and is reacted.When in reaction kettle
It is continuous in 3.0 hours, be homogeneously added into acrylic ester monomer and remaining vinyl chloride when pressure reduction 0.2MPa, continue
Reaction:
When the pressure in reaction kettle is down to 0.25MPa or less, the temperature of charge in reaction kettle is risen to 73 degrees Celsius, and herein
At a temperature of keep the temperature 1.5 hours;
Later, the material in reaction kettle is poured out, centrifugal drier is used in combination to be dehydrated;
Later, to being washed through dewatered material;
Later, second dehydration is carried out to the material after washed with centrifugal drier;
Later, with 45 degrees Celsius of hot wind to being dried into the material through second dehydration;
Finally, the material after drying is sieved with the sieve of 40 mesh, vinyl chloride high polymer is made.
Embodiment three
First choose the vinyl chloride of 65 parts by weight, the acrylic ester monomer of 15 parts by weight, the vinylacetate of 5 parts by weight, 0.5 weight
Measure the molecular weight regulator of part, the initiator of 1.2 parts by weight, 10 parts by weight dispersant and 90 parts by weight deionized water.
Wherein:
Acrylic ester monomer is ethyl acrylate, butyl acrylate, Isooctyl acrylate monomer, methyl methacrylate and according to third
Olefin(e) acid ethyl ester:Butyl acrylate:Isooctyl acrylate monomer:Methyl methacrylate=1: 3: 1:2 weight ratio mixes;
The molecular weight regulator is to use diallyl maleate, diallyl phthalate, butanediol diacrylate simultaneously
According to diallyl maleate:Diallyl phthalate:Butanediol diacrylate=2: 2:1 weight ratio mixing
It forms;
The initiator is to use dicetyl peroxydicarbonate(2- ethyls)Ethyl ester and cumyl peroxyneodecanoate and according to peroxidating
Two carbonic acid(2- ethyls)Ethyl ester:Cumyl peroxyneodecanoate=2:1 weight ratio mixes.
The dispersant is with polyvinyl alcohol and polyvinylpyrrolidone methylcellulose graft copolymer and according to poly-
Vinyl alcohol:Polyvinylpyrrolidone methylcellulose graft copolymer=1:3 weight ratio mixes.
Then, molecular weight regulator, initiator, dispersant and deionized water are added in reaction kettle, while agitating,
Reaction kettle is vacuumized, dispersant is made fully to dissolve;
While continuing stirring, vinylacetate is added;Later, it is added the 3/5 of vinyl chloride, and continues stirring 30 minutes, is made
Starting material is pre-dispersed;
Later, reaction kettle is heated, so that the material in reaction kettle is warming up to 60 degrees Celsius and is reacted.When in reaction kettle
It is continuous in 3.1 hours, be homogeneously added into acrylic ester monomer and remaining vinyl chloride when pressure reduction 0.2MPa, continue
Reaction:
When the pressure in reaction kettle is down to 0.25MPa or less, the temperature of charge in reaction kettle is risen to 75 degrees Celsius, and herein
At a temperature of keep the temperature 2 hours;
Later, the material in reaction kettle is poured out, centrifugal drier is used in combination to be dehydrated;
Later, to being washed through dewatered material;
Later, second dehydration is carried out to the material after washed with centrifugal drier;
Later, with 50 degrees Celsius of hot wind to being dried into the material through second dehydration;
Finally, the material after drying is sieved with the sieve of 40 mesh, vinyl chloride high polymer is made.
Claims (7)
1. a kind of vinyl chloride high polymer, it is characterised in that be made of following raw material:
45 ~ 65 parts by weight of vinyl chloride;
5 ~ 25 parts by weight of acrylic ester monomer;
5 ~ 15 parts by weight of vinylacetate;
0.01 ~ 0.5 parts by weight of molecular weight regulator;
0.2 ~ 1.2 parts by weight of initiator;
2 ~ 10 parts by weight of dispersant;
90 ~ 120 parts by weight of deionized water.
2. vinyl chloride high polymer according to claim 1, it is characterised in that the acrylics monomer is acrylic acid second
Two or more mixtures of ester, butyl acrylate, Isooctyl acrylate monomer and ethyl methacrylate.
3. vinyl chloride high polymer according to claim 1, it is characterised in that the acrylics monomer is to use acrylic acid
Ethyl ester, butyl acrylate and methyl methacrylate and according to ethyl acrylate:Butyl acrylate:Methyl methacrylate=1:
3: 1:2 weight ratio mixes.
4. vinyl chloride high polymer according to claim 1, it is characterised in that the molecular weight regulator is to use maleic acid two
Allyl ester, diallyl phthalate and butanediol diacrylate and according to diallyl maleate:Phthalic acid two
Allyl ester:Butanediol diacrylate=2:2:1 weight ratio mixes.
5. vinyl chloride high polymer according to claim 1, it is characterised in that the initiator is to use dicetyl peroxydicarbonate(2-
Ethyl)Ethyl ester and cumyl peroxyneodecanoate and according to dicetyl peroxydicarbonate(2- ethyls)Ethyl ester:Peroxidating neodecanoic acid is different
Propyl benzene ester=2:1 weight ratio mixes.
6. vinyl chloride high polymer according to claim 1, it is characterised in that the dispersant is to use polyvinyl alcohol and poly- second
Vinyl pyrrolidone methylcellulose graft copolymer and according to polyvinyl alcohol:Polyvinylpyrrolidone methylcellulose is grafted
Copolymer=1:3 weight ratio mixes.
7. the method for preparing vinyl chloride high polymer described in claim 1, it is characterised in that include the following steps successively:
First molecular weight regulator, initiator, dispersant and deionized water are added in reaction kettle, while agitating, to reaction
Kettle is vacuumized, and dispersant is made fully to dissolve;
While continuing stirring, vinylacetate is added;Later, the 1/2-2/3 of vinyl chloride is added, and continues to stir 20-30
Minute, keep starting material pre-dispersed;
Later, reaction kettle is heated, so that the material in reaction kettle is warming up to 40-60 degrees Celsius and is reacted;Work as reaction kettle
It is continuous in 2.9 ~ 3.1 hours, be homogeneously added into acrylic ester monomer and remaining chloroethene when interior pressure reduction 0.2MPa
Alkene;
When the pressure in reaction kettle is down to 0.25MPa or less, the temperature of charge in reaction kettle is risen to 70-75 degrees Celsius, and
Keep the temperature 1-2 hours at this temperature;
Later, the material in reaction kettle is poured out and is dehydrated;
Later, to being washed through dewatered material;
Later, second dehydration is carried out to the material after washed;
Later, with 40-50 DEG C of hot wind to being dried into the material through second dehydration;
Finally, the material after drying is sieved with the sieve of 40 mesh, vinyl chloride high polymer is made.
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Cited By (5)
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CN111333765A (en) * | 2020-04-03 | 2020-06-26 | 无锡洪汇新材料科技股份有限公司 | Vinyl chloride-vinyl acetate-acrylic acid-2-ethylhexyl ester copolymer resin and preparation method thereof |
CN111471246A (en) * | 2020-04-03 | 2020-07-31 | 无锡洪汇新材料科技股份有限公司 | Environment-friendly toughening type PVC electrical casing processing modifier and preparation method thereof |
JP2020169427A (en) * | 2019-04-05 | 2020-10-15 | アキレス株式会社 | Synthetic leather having anti-fouling performance |
CN112409543A (en) * | 2020-10-26 | 2021-02-26 | 安徽天辰化工股份有限公司 | Preparation method of vinyl chloride and acrylate copolymer emulsion |
CN113321759A (en) * | 2021-06-10 | 2021-08-31 | 泰州市正大化工有限公司 | Preparation method of low-viscosity vinyl chloride-vinyl acetate copolymer |
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Cited By (8)
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JP2020169427A (en) * | 2019-04-05 | 2020-10-15 | アキレス株式会社 | Synthetic leather having anti-fouling performance |
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CN111471246A (en) * | 2020-04-03 | 2020-07-31 | 无锡洪汇新材料科技股份有限公司 | Environment-friendly toughening type PVC electrical casing processing modifier and preparation method thereof |
CN111471246B (en) * | 2020-04-03 | 2021-11-02 | 无锡洪汇新材料科技股份有限公司 | Environment-friendly toughening type PVC electrical casing processing modifier and preparation method thereof |
CN111333765B (en) * | 2020-04-03 | 2021-11-02 | 无锡洪汇新材料科技股份有限公司 | Vinyl chloride-vinyl acetate-acrylic acid-2-ethylhexyl ester copolymer resin and preparation method thereof |
CN112409543A (en) * | 2020-10-26 | 2021-02-26 | 安徽天辰化工股份有限公司 | Preparation method of vinyl chloride and acrylate copolymer emulsion |
CN113321759A (en) * | 2021-06-10 | 2021-08-31 | 泰州市正大化工有限公司 | Preparation method of low-viscosity vinyl chloride-vinyl acetate copolymer |
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