CN110144030A - A kind of MABS polymer and preparation method thereof - Google Patents
A kind of MABS polymer and preparation method thereof Download PDFInfo
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- CN110144030A CN110144030A CN201910344936.9A CN201910344936A CN110144030A CN 110144030 A CN110144030 A CN 110144030A CN 201910344936 A CN201910344936 A CN 201910344936A CN 110144030 A CN110144030 A CN 110144030A
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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
- C08F285/00—Macromolecular compounds obtained by polymerising monomers on to preformed graft polymers
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L27/00—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Compositions of derivatives of such polymers
- C08L27/22—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 modified by chemical after-treatment
- C08L27/24—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 modified by chemical after-treatment halogenated
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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
- C08L51/00—Compositions of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers
- C08L51/003—Compositions of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers grafted on to macromolecular compounds obtained by reactions only involving unsaturated carbon-to-carbon bonds
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Abstract
The present invention relates to a kind of MABS polymer and preparation method thereof, content meter includes: 30-70% stratum nucleare polymer, 20-60% sheath polymers and 10% grafting MMA to the polymer by mass percentage；The grafting MMA is coated on outside shell；The stratum nucleare polymer is PB rubber particles, and the sheath polymers are SAN graft copolymer.The present invention in preparation by using specific emulsifier and molecular weight regulator, to improve the interface binding power between copolymer and matrix, so that the MABS polymer of preparation is can be used as graft copolymer modifying agent and matrix CPVC better compatibility, can be more uniform be dispersed in matrix CPVC, and then improve material comprehensive performance.
Description
Technical field
The present invention relates to technical field of polymer materials, specifically, being related to a kind of MABS polymer and preparation method thereof.
Background technique
MABS, methyl methacrylate-acrylonitrile-butadiene-polyglass are that common ABS addition PMMA is done
The ABS of transparency levels out.Transparent ABS Resin is grown up on the basis of general ABS resin, which has
While good light permeability, the advantages such as impact flexibility also with higher and the lower market price be used to produce large screen
A variety of high-grade transparent articles such as the protection screen of color TV, and have become a kind of irreplaceable novel height of other transparent plastics
Molecular material.
Summary of the invention
In view of the drawbacks of the prior art, the object of the present invention is to provide a kind of CPVC/MABS compositions and preparation method thereof.
The purpose of the present invention is what is be achieved through the following technical solutions:
The present invention provides a kind of MABS polymer, by mass percentage content meter include: 30-70% stratum nucleare polymer,
20-60% sheath polymers and 10% grafting MMA；The grafting MMA is coated on outside shell；The stratum nucleare polymer is PB rubber
Particle, the sheath polymers are SAN graft copolymer.
Preferably, the preparation method of the MABS polymer includes the following steps:
A1, by deionized water, glucose, sodium pyrophosphate after completely dissolution, be added ferrous sulfate, PB latex, emulsifier, hydrogen
Potassium oxide, stirring in water bath；
A2, after step A1 processing, the mixing list that is made of styrene, acrylonitrile, initiator, molecular weight regulator is added dropwise
Body, reaction；
A3, step A2 methyl methacrylate is added dropwise again after reaction, initiator is reacted, antioxygen is then added
Agent is demulsified after stirring, is agglomerated, is dehydrated, is dried, and MABS graft copolymer modifying agent is obtained.
Preferably, the initiator is cumyl hydroperoxide；The molecular weight regulator is tert-dodecylmercaotan
(TDDM)。
Preferably, the emulsifier includes each component of following mass percentage:
RA rosin acid 3-4.5%；PH value adjustment agent 0.05-0.1%；Fatty acid 0.2-1%；Electrolyte 1.5-3%；12
Sodium alkyl benzene sulfonate 0.1-0.5%；Water surplus.
Preferably, the electrolyte includes potassium carbonate and sodium sulphate；The mass percentage of the potassium carbonate is 1-2%,
The mass percentage of sodium sulphate is 0.5-1%.
Preferably, the additional amount of the emulsifier is the 1-6% of MABS graft copolymer modifying agent gross mass.
Preferably, in step A1, the bath temperature is 60-70 DEG C, stirring carries out under N2 protection, N2Being passed through the time is
10-30min；
In step A2, the reaction temperature is 60-70 DEG C, reaction time 0.5-3h；
In step A3, the reaction temperature is 60-70 DEG C, reaction time 0.5-3h, and the mixing time is 10-
30min。
The present invention provides a kind of preparation methods of CPVC/MABS composition, comprising the following steps:
MABS polymer and CPVC matrix resin are subjected to melt blending in proportion to get the CPVC/MABS composition.
Preferably, the temperature of the melt blending is 170-180 DEG C, the time is 5-10 minutes.
Compared with prior art, the present invention have it is following the utility model has the advantages that
1, in MABS polymer of the invention preparation, specific emulsifier is used, copolymer and matrix tree can be improved
Interface binding power between rouge, and then improve the comprehensive performance of material.
2, specific molecular weight regulator TDDM is added in MABS polymer of the invention preparation, by point for adjusting MABS
Son amount, so that the changeable compatibility with CPVC matrix resin, further improves the interface binding power of polymer and matrix resin,
The toughness of blend is improved significantly, improves 20% or more.
3, the present invention is by emulsion polymerization the compounding design novel MABS polymer with three-decker, stratum nucleare
PB, middle layer SAN, outermost layer PMMA.Using the MABS polymer as graft copolymer modifying agent, can have with matrix CPVC
Better compatibility, can be more uniform be dispersed in matrix CPVC.The mechanical property of thus obtained CPVC/MABS composition
It can significantly improve.
Specific embodiment
The present invention is described in detail combined with specific embodiments below.Following embodiment will be helpful to the technology of this field
Personnel further understand the present invention, but the invention is not limited in any way.It should be pointed out that the ordinary skill of this field
For personnel, without departing from the inventive concept of the premise, various modifications and improvements can be made.These belong to the present invention
Protection scope.
Following embodiment provides a kind of MABS polymer, and content meter includes: the polymerization of 30-70% stratum nucleare by mass percentage
Object, 20-60% sheath polymers and 10% grafting MMA；The grafting MMA is coated on outside shell；The stratum nucleare polymer is PB
Rubber particles, the sheath polymers are SAN graft copolymer.
The preparation method of the MABS polymer includes the following steps:
A1, by deionized water, glucose, sodium pyrophosphate after completely dissolution, be added ferrous sulfate, PB latex, emulsifier, hydrogen
Potassium oxide, stirring in water bath；
A2, after step A1 processing, the mixing list that is made of styrene, acrylonitrile, initiator, molecular weight regulator is added dropwise
Body, reaction；
A3, step A2 methyl methacrylate is added dropwise again after reaction, initiator is reacted, antioxygen is then added
Agent is demulsified after stirring, is agglomerated, is dehydrated, is dried, and MABS graft copolymer modifying agent is obtained.
The initiator is cumyl hydroperoxide；The molecular weight regulator is TDDM.
The emulsifier includes each component of following mass percentage:
RA rosin acid 3-4.5%；PH value adjustment agent 0.05-0.1%；Fatty acid 0.2-1%；Electrolyte 1.5-3%；12
Sodium alkyl benzene sulfonate 0.1-0.5%；Water surplus.
The electrolyte includes potassium carbonate and sodium sulphate；The mass percentage of the potassium carbonate is 1-2%, sodium sulphate
Mass percentage is 0.5-1%.
The additional amount of the emulsifier is the 1-6% of MABS graft copolymer modifying agent gross mass.
In step A1, the bath temperature is 60-70 DEG C, stirring is in N2Protection is lower to be carried out, N2Being passed through the time is 10-
30min；
In step A2, the reaction temperature is 60-70 DEG C, reaction time 0.5-3h；
In step A3, the reaction temperature is 60-70 DEG C, reaction time 0.5-3h, and the mixing time is 10-
30min。
Following embodiment additionally provides a kind of preparation method of CPVC/MABS composition, comprising the following steps:
MABS graft copolymer modifying agent and CPVC matrix resin are subjected to melt blending in proportion to get the CPVC/
MABS composition.The CPVC/MABS composition, each component including following weight percent:
CPVC matrix resin 50-78.6%；
MABS graft copolymer modifying agent 21.4-50%.
The temperature of the melt blending is 170-180 DEG C, the time is 5-10 minutes.
Embodiment 1
A kind of preparation method of MABS polymer is present embodiments provided, steps are as follows:
100ml deionized water, 0.6g DX, 0.4g SPP is added after completely dissolution in 1000ml there-necked flask, is then added
10ml FES (1mg/ml), 55g PBL (55%), 3g emulsifier (for the 3% of MABS total amount), 0.05g KOH, are placed in 65 DEG C of perseverances
In tepidarium, lead to N2It protects and stirs, after twenty minutes, be then added dropwise by 45g St, 15g AN, 0.60ml CHP, molecular weight tune
The mix monomer of agent TDDM 0.05ml composition is saved, adds CHP 0.05ml before being added dropwise, time for adding 1.5h is added dropwise
0.05ml CHP is added to reaction system again, then after reacting 1h, 10g MMA monomer, 0.15ml CHP, 0.05ml TDDM is added dropwise
The mix monomer of composition time for adding 15 minutes, reacts 1 hour, is cooled to 50 DEG C after reaction hereinafter, 5ml antioxygen is added
Agent, continues stirring 20 minutes, and discharging is added flocculant concentrated sulfuric acid 1ml, is demulsified, agglomerated, be dehydrated, dried, obtained MABS and connect
Graft copolymer modifying agent.
Wherein the emulsifier the preparation method is as follows:
The weight percent of first according to the form below prepares each component, and rosin soap lye is dissolved in solvent and forms rosin soap lye (pine
In perfumed soap liquid 25%) RA rosin acid content is, potassium hydroxide is configured to solution, then by rosin soap lye, sodium hydroxide solution, rouge
Fat acid, potassium carbonate, sodium sulphate, neopelex be added to the water carry out physical mixed to get.
MABS polymer manufactured in the present embodiment is used for the preparation of CPVC/MABS composition, steps are as follows:
MABS graft copolymer modifying agent 50 grams (50%) prepared by step 1 and 50 grams of CPVC matrix resin (50%) into
Row melt blending, temperature is 170-180 DEG C, the time is 5-10 minutes, and CPVC/MABS composition is made.
There are many concrete application approach of the present invention, the above is only a preferred embodiment of the present invention.More than it should be pointed out that
Embodiment is merely to illustrate the present invention, and the protection scope being not intended to restrict the invention.For the common skill of the art
For art personnel, without departing from the principle of the present invention, several improvement can also be made, these improvement also should be regarded as this hair
Bright protection scope.
Claims (7)
1. a kind of MABS polymer, which is characterized in that content meter includes: 30-70% stratum nucleare polymer, 20- by mass percentage
60% sheath polymers and 10% grafting MMA；The grafting MMA is coated on outside shell；The stratum nucleare polymer is PB rubber granule
Son, the sheath polymers are SAN graft copolymer.
2. a kind of preparation method of MABS polymer according to claim 1, which comprises the steps of:
A1, by deionized water, glucose, sodium pyrophosphate after completely dissolution, be added ferrous sulfate, PB latex, emulsifier, hydroxide
Potassium, stirring in water bath；
A2, after step A1 processing, the mix monomer that is made of styrene, acrylonitrile, initiator, molecular weight regulator is added dropwise,
Reaction；
The mixing that methyl methacrylate, initiator and molecular weight regulator composition is added dropwise again after reaction of A3, step A2
Monomer is reacted, and antioxidant is then added, is demulsified, agglomerated, be dehydrated, dried after stirring, MABS graft copolymer is obtained
Modifying agent.
3. the preparation method of MABS polymer according to claim 2, which is characterized in that the initiator is hydrogen peroxide
Isopropylbenzene；The molecular weight regulator is tert-dodecylmercaotan.
4. the preparation method of MABS polymer according to claim 2, which is characterized in that the emulsifier includes following matter
Measure each component of percentage composition:
RA rosin acid 3-4.5%；PH value adjustment agent 0.05-0.1%；Fatty acid 0.2-1%；Electrolyte 1.5-3%；Dodecyl
Benzene sulfonic acid sodium salt 0.1-0.5%；Water surplus.
5. the preparation method of MABS polymer according to claim 4, which is characterized in that the electrolyte includes potassium carbonate
And sodium sulphate；The mass percentage of the potassium carbonate is 1-2%, and the mass percentage of sodium sulphate is 0.5-1%.
6. according to the preparation method of MABS alloy material described in claim 2,4 or 5, which is characterized in that the emulsifier
Additional amount is the 1-6% of MABS graft copolymer modifying agent gross mass.
7. the preparation method of MABS polymer according to claim 3, which is characterized in that in step A1, the water-bath temperature
Degree is 60-70 DEG C, stirring is in N2Protection is lower to be carried out, N2Being passed through the time is 10-30min；
In step A2, the reaction temperature is 60-70 DEG C, reaction time 0.5-3h；
In step A3, the reaction temperature is 60-70 DEG C, reaction time 0.5-3h, and the mixing time is 10-30min.
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Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN115028782A (en) * | 2021-03-08 | 2022-09-09 | 中国石油天然气股份有限公司 | Method for preparing fluorine-containing high-weather-resistance thermoplastic resin by emulsion polymerization and prepared thermoplastic resin |
| CN115043996A (en) * | 2021-03-08 | 2022-09-13 | 中国石油天然气股份有限公司 | Method for preparing high-weather-resistance thermoplastic resin by emulsion polymerization and prepared silicon-containing thermoplastic resin |
| CN115043991A (en) * | 2021-03-08 | 2022-09-13 | 中国石油天然气股份有限公司 | Method for preparing fluorine-containing thermoplastic elastomer by emulsion polymerization method and prepared thermoplastic elastomer |
| CN115043980A (en) * | 2021-03-08 | 2022-09-13 | 中国石油天然气股份有限公司 | Method for preparing cold-resistant thermoplastic elastomer by emulsion polymerization method and prepared silicon-containing thermoplastic elastomer |
| CN115043992A (en) * | 2021-03-08 | 2022-09-13 | 中国石油天然气股份有限公司 | Thermoplastic elastomer with improved hardness and preparation method thereof |
| CN115043995A (en) * | 2021-03-08 | 2022-09-13 | 中国石油天然气股份有限公司 | Method for preparing thermoplastic resin by emulsion polymerization method and prepared thermoplastic resin |
| CN115043997A (en) * | 2021-03-08 | 2022-09-13 | 中国石油天然气股份有限公司 | Method for preparing carboxyl-containing thermoplastic elastomer by emulsion polymerization method and prepared thermoplastic elastomer |
| CN115043994A (en) * | 2021-03-08 | 2022-09-13 | 中国石油天然气股份有限公司 | Emulsion polymerization preparation method of thermoplastic resin with improved heat resistance and thermoplastic resin obtained by emulsion polymerization preparation method |
| CN115043993A (en) * | 2021-03-08 | 2022-09-13 | 中国石油天然气股份有限公司 | Method for preparing carboxyl-containing thermoplastic resin by emulsion polymerization method and prepared carboxyl-containing thermoplastic resin |
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Cited By (18)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN115028782A (en) * | 2021-03-08 | 2022-09-09 | 中国石油天然气股份有限公司 | Method for preparing fluorine-containing high-weather-resistance thermoplastic resin by emulsion polymerization and prepared thermoplastic resin |
| CN115043996A (en) * | 2021-03-08 | 2022-09-13 | 中国石油天然气股份有限公司 | Method for preparing high-weather-resistance thermoplastic resin by emulsion polymerization and prepared silicon-containing thermoplastic resin |
| CN115043991A (en) * | 2021-03-08 | 2022-09-13 | 中国石油天然气股份有限公司 | Method for preparing fluorine-containing thermoplastic elastomer by emulsion polymerization method and prepared thermoplastic elastomer |
| CN115043980A (en) * | 2021-03-08 | 2022-09-13 | 中国石油天然气股份有限公司 | Method for preparing cold-resistant thermoplastic elastomer by emulsion polymerization method and prepared silicon-containing thermoplastic elastomer |
| CN115043992A (en) * | 2021-03-08 | 2022-09-13 | 中国石油天然气股份有限公司 | Thermoplastic elastomer with improved hardness and preparation method thereof |
| CN115043995A (en) * | 2021-03-08 | 2022-09-13 | 中国石油天然气股份有限公司 | Method for preparing thermoplastic resin by emulsion polymerization method and prepared thermoplastic resin |
| CN115043997A (en) * | 2021-03-08 | 2022-09-13 | 中国石油天然气股份有限公司 | Method for preparing carboxyl-containing thermoplastic elastomer by emulsion polymerization method and prepared thermoplastic elastomer |
| CN115043994A (en) * | 2021-03-08 | 2022-09-13 | 中国石油天然气股份有限公司 | Emulsion polymerization preparation method of thermoplastic resin with improved heat resistance and thermoplastic resin obtained by emulsion polymerization preparation method |
| CN115043993A (en) * | 2021-03-08 | 2022-09-13 | 中国石油天然气股份有限公司 | Method for preparing carboxyl-containing thermoplastic resin by emulsion polymerization method and prepared carboxyl-containing thermoplastic resin |
| CN115043980B (en) * | 2021-03-08 | 2023-06-30 | 中国石油天然气股份有限公司 | Method for preparing cold-resistant thermoplastic elastomer by emulsion polymerization method and prepared silicon-containing thermoplastic elastomer |
| CN115043993B (en) * | 2021-03-08 | 2023-06-30 | 中国石油天然气股份有限公司 | Method for preparing carboxyl-containing thermoplastic resin by emulsion polymerization method and prepared carboxyl-containing thermoplastic resin |
| CN115043992B (en) * | 2021-03-08 | 2023-06-30 | 中国石油天然气股份有限公司 | Thermoplastic elastomer with improved hardness and preparation method thereof |
| CN115043995B (en) * | 2021-03-08 | 2023-06-30 | 中国石油天然气股份有限公司 | Method for preparing thermoplastic resin by emulsion polymerization method and thermoplastic resin prepared by same |
| CN115028782B (en) * | 2021-03-08 | 2023-07-25 | 中国石油天然气股份有限公司 | Method for preparing fluorine-containing high-weather-resistance thermoplastic resin by emulsion polymerization method and prepared thermoplastic resin |
| CN115043997B (en) * | 2021-03-08 | 2023-07-25 | 中国石油天然气股份有限公司 | Method for preparing carboxyl-containing thermoplastic elastomer by emulsion polymerization method and prepared thermoplastic elastomer |
| CN115043996B (en) * | 2021-03-08 | 2023-07-25 | 中国石油天然气股份有限公司 | Method for preparing high-weather-resistance thermoplastic resin by emulsion polymerization method and prepared silicon-containing thermoplastic resin |
| CN115043991B (en) * | 2021-03-08 | 2023-07-25 | 中国石油天然气股份有限公司 | Method for preparing fluorine-containing thermoplastic elastomer by emulsion polymerization method and prepared thermoplastic elastomer |
| CN115043994B (en) * | 2021-03-08 | 2023-07-25 | 中国石油天然气股份有限公司 | Emulsion polymerization preparation method of thermoplastic resin with improved heat resistance and thermoplastic resin obtained by emulsion polymerization preparation method |
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