CN109666102B - A kind of the ASA graft copolymer and preparation method of chemical modification efficient heat-resisting - Google Patents
A kind of the ASA graft copolymer and preparation method of chemical modification efficient heat-resisting Download PDFInfo
- Publication number
- CN109666102B CN109666102B CN201811617117.9A CN201811617117A CN109666102B CN 109666102 B CN109666102 B CN 109666102B CN 201811617117 A CN201811617117 A CN 201811617117A CN 109666102 B CN109666102 B CN 109666102B
- Authority
- CN
- China
- Prior art keywords
- asa
- graft copolymer
- added
- deionized water
- latex
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
Classifications
-
- 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
- C08F265/00—Macromolecular compounds obtained by polymerising monomers on to polymers of unsaturated monocarboxylic acids or derivatives thereof as defined in group C08F20/00
- C08F265/04—Macromolecular compounds obtained by polymerising monomers on to polymers of unsaturated monocarboxylic acids or derivatives thereof as defined in group C08F20/00 on to polymers of esters
-
- 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
- C08F212/00—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 aromatic carbocyclic ring
- C08F212/02—Monomers containing only one unsaturated aliphatic radical
- C08F212/04—Monomers containing only one unsaturated aliphatic radical containing one ring
- C08F212/06—Hydrocarbons
- C08F212/08—Styrene
Landscapes
- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Graft Or Block Polymers (AREA)
Abstract
The present invention discloses the ASA graft copolymer and preparation method of a kind of chemical modification efficient heat-resisting, and it is lower to solve the copolymer-modified efficiency of ASA in the prior art, on the big problem of the influences such as product impact, appearance.A kind of preparation method of the ASA graft copolymer of chemical modification efficient heat-resisting of the invention, using the phenyl siloxane rubber lotion of crosslinking as seed, after being coated with acrylic rubber to it, ASA graft copolymer is made in graft phenylethene, acrylonitrile；Wherein, phenyl siloxane rubber has acrylate group, and the mass percent that phenyl siloxane rubber accounts for ASA graft copolymer is 10%-40%.Design science of the present invention, method is simple, easy to operate, can be obviously improved ASA copolymer heat resistance, and heat-resisting system is more stable, more efficient, good-toughness, and does not influence material appearance.
Description
Technical field
The invention belongs to chemical synthesis modified new-material technical fields, and in particular to a kind of chemical modification efficient heat-resisting
ASA graft copolymer and preparation method.
Background technique
Acrylonitrile-styrene-acrylic ester copolymer have excellent mouldability, weatherability, good toughness, but heat resistance compared with
Difference is unable to satisfy part high heat resistance application demand.In the prior art, substantially all by adding heat-resisting change during physical blending
Property agent promotes product heat resistance, but modification efficiency is lower, big on influences such as product impact, appearances.
Therefore it provides a kind of preparation method of ASA graft copolymer, easy to operate, modification efficiency is high, and heat-resisting system is more steady
Fixed, good-toughness becomes those skilled in the art's urgent problem to be solved.
Summary of the invention
Technical problem solved by the present invention is providing a kind of preparation of the ASA graft copolymer of chemical modification efficient heat-resisting
Method, the copolymer-modified efficiency of ASA is lower in the prior art for solution, on the big problem of the influences such as product impact, appearance.
The present invention also provides using ASA graft copolymer made from the preparation.
The technical solution adopted by the invention is as follows:
The preparation method of the ASA graft copolymer of a kind of chemical modification efficient heat-resisting of the present invention, with the benzene of crosslinking
Base silicon rubber lotion is seed, and after being coated with acrylic rubber to it, the ASA is made in graft phenylethene, acrylonitrile
Graft copolymer；Wherein, the phenyl siloxane rubber has acrylate group, and the phenyl siloxane rubber accounts for the ASA grafting altogether
The mass percent of polymers is 10%-40%.
Further, comprising the following steps:
Step 1. prepares organosilicon pre-emulsion: phenyl siloxane monomer being added into reactor, the first crosslinking agent, contains propylene
The silane coupling agent of perester radical, emulsifier, deionized water emulsify in mulser after stirring and organosilicon pre-emulsion are made,
Deionized water is added in the reactor with blender, stirs, the pre- cream of the organosilicon is continuously added dropwise in heating
Liquid is added dropwise, then heats up, and reaction a period of time, obtains organic silicon emulsion；
Step 2. prepares PBA base latex: the cream of organosilicon made from step 1 being added into the reactor equipped with blender
Liquid adds deionized water, emulsifier, inorganic initiator, stirs, heating, continuous to be added dropwise containing organic peroxy initiator, the
The mix monomer of two crosslinking agents, acrylate monomer, is added dropwise, then heats up, and reaction a period of time, obtains PBA base latex；
Step 3. prepares mix monomer lotion: organic peroxy initiator, chain-transferring agent, benzene second being added into reactor
Mix monomer lotion is made in alkene, acrylonitrile, emulsifier, deionized water, stirring；
Step 4. prepares ASA latex: PBA base latex made from step 2 is added into the reactor equipped with blender, then
Deionized water, emulsifier, inorganic initiator is added, stirs, heats up, mix monomer lotion made from continuous a dropping step 3 is added dropwise
It to finishing, then heats up, reaction a period of time, obtains ASA latex；
ASA latex made from step 4 through demulsification, cohesion, washing, filtering, drying, is obtained ASA graft copolymerization by step 5.
Object.
Further, phenyl siloxane monomer, the first crosslinking agent in the step 1, containing acrylate-based alkoxyl silicone
Alkane, emulsifier, deionized water weight ratio be 10~30:0.1~1:0.4~2:1~4:50~200.
Further, organic silicon emulsion, deionized water, emulsifier, inorganic initiator, organic peroxy in the step 2
Initiator, the second crosslinking agent, acrylate monomer weight ratio be 10~40:100~150:0.1~0.5:0.5~2:0.1~
1.0:0.5~2.5:20~50, wherein organic silicon emulsion is with solid meter.
Further, in the step 3, organic peroxy initiator, chain-transferring agent, styrene, acrylonitrile, emulsifier,
The weight ratio of deionized water is 0.1~1.0:0.05~0.25:10~35:15~40:0.1~0.5:50~150；
In the step 4, PBA base latex, deionized water, the weight ratio of inorganic initiator are 50~60:150~250:
0.1~0.5；Wherein PBA base latex is with solid meter.
Further, in the step 1, when preparing organosilicon pre-emulsion, prior to after stirring at normal temperature 30-60min then at cream
5-10min is emulsified with the speed strength of 5000-10000r/min in change machine；Deionization is added in the reactor with blender
Water, hydrochloric acid, stirring, and it is warming up to 50-60 DEG C, and it is continuous that prepared organosilicon pre-emulsion in advance is added dropwise, it is at the uniform velocity added dropwise to and finishes,
It is warming up to 80-90 DEG C again, reacts 3-4h, obtains organic silicon emulsion.
Further, in the step 2, organic silicon emulsion made from step 1 is added into the reactor equipped with blender,
Deionized water, emulsifier, inorganic initiator are added, is stirred, is warming up to 50-60 DEG C, the mix monomer is continuously added dropwise, at the uniform velocity
After being added dropwise, then it is warming up to 80-90 DEG C, reacts 3-4h, obtain PBA base latex.
Further, in the step 3, the condition of stirring is stirring at normal temperature 30-60min；
Or/and in the step 4, PBA base latex made from step 2 is added into the reactor equipped with blender, then
Deionized water, emulsifier, inorganic initiator is added, stirring is warming up to 50-60 DEG C, mix monomer made from continuous a dropping step 3
Lotion is at the uniform velocity added dropwise to and finishes, then is warming up to 80-90 DEG C, reacts 3-4h, obtains ASA latex.
Further, the phenyl siloxane monomer is the siloxanes ring body containing phenyl, is selected from trimethyl triphenyl ring three
Any one or a few in siloxanes, tetramethyl tetraphenyl cyclotetrasiloxane；
Or/and first crosslinking agent is containing the siloxanyl monomers for being more than or equal to two alkoxies；
Or/and it is described containing acrylate-based silane coupling agent be methacryloxypropyl trimethoxy silane, first
Any one or a few in base acryloxypropyl triethoxysilane；
Or/and the acrylate monomer is any in ethyl acrylate, butyl acrylate or Isooctyl acrylate monomer
It is one or more of；
Or/and the emulsifier is selected from neopelex, lauryl sodium sulfate, dodecyl sodium sulfate, alkane
The mixture of one or more of base phenol polyethenoxy base ether；
Or/and the organic peroxide evocating agent is selected from cumyl hydroperoxide, cumyl peroxide, the peroxidating moon
Any one or a few in osmanthus acyl, peroxidized t-butyl perbenzoate；
Or/and second crosslinking agent be selected from ethylene glycol diacrylate, butanediol diacrylate, diacrylate oneself two
Alcohol ester, in any one or a few；
Or/and the inorganic initiator is one or more of in ammonium persulfate, potassium peroxydisulfate, sodium peroxydisulfate；
Or/and the chain-transferring agent in n- dodecyl mereaptan, tert-dodecyl mercaptan, n-octyl mercaptan any one or it is several
Kind.
Using ASA graft copolymer made from above-mentioned preparation method.
Compared with prior art, the invention has the following advantages:
Design science of the present invention, method is simple, easy to operate.Using phenyl siloxane rubber as seed, then with acrylic rubber
Cladding, last graft phenylethene, acrylonitrile can be obviously improved ASA copolymer heat resistance, and heat-resisting system is more stable, efficiency
It is higher, good-toughness.The heat-proof modifier of same ratio is added, ASA graft copolymer of the invention is produced than conventional blending and modifying
The heat-resisting promotion effect of product is more preferable, and impact property is higher, and does not influence material appearance.
ASA graft copolymer resin rubber powder provided by the invention can not only be used for raw material sale, can also be applied to ASA and its conjunction
The preparation of golden modified resin.The ASA graft copolymer resin rubber powder obtained using preparation method of the present invention, can be with AS, PC, PMMA
Equal blendings are granulated, and multi items, the ASA of polytypic and its alloy modification resin finished product are prepared, to meet different market needs.
Specific embodiment
Below with reference to embodiment, the invention will be further described, and mode of the invention includes but are not limited to following implementation
Example.
Embodiment 1
Present embodiment discloses the preparation of ASA graft copolymer of the invention, specifically:
The preparation of step 1. organosilicon pre-emulsion: trimethyl triphenyl cyclotrisiloxane 30g, dioxane are added into reactor
Oxygroup siloxanes 0.3g, methacryloxypropyl trimethoxy silane 0.5g, dodecyl sodium sulfate 2g, deionized water
150g, stirring at normal temperature 40min are placed into mulser and are emulsified 5min with the speed strength of 6000r/min, and the pre- cream of organosilicon is made
Liquid；
Deionized water 50g stirring is added in the reactor with blender, and is warming up to 60 DEG C, continuous be added dropwise is matched in advance
The organosilicon pre-emulsion made, is at the uniform velocity added dropwise to and finishes, then is warming up to 90 DEG C, reacts 4h, obtains organic silicon emulsion；
Step 2. prepares PBA base latex: the cream of organosilicon obtained in step 1 being added into the reactor equipped with blender
Liquid 10g, then add into deionized water 100g, dodecyl sodium sulfate 0.3g, potassium peroxydisulfate 1g, stirring, and be warming up to 60 DEG C, even
Continuous dropwise addition is prepared in advance to contain cumyl hydroperoxide 0.5g, butanediol diacrylate 1.5g, Butyl Acrylate Monomer
The mix monomer of 50g, is at the uniform velocity added dropwise to and finishes, then is warming up to 90 DEG C, reacts 4h, obtains PBA base latex；Wherein organosilicon cream
Liquid is with solid meter.
Step 3. prepares mix monomer lotion: cumyl hydroperoxide 0.5g, n- dodecyl mereaptan being added into reactor
0.1g, styrene 10g, acrylonitrile 30g, dodecyl sodium sulfate 0.3g, deionized water 100g, stirring at normal temperature 40min are made mixed
Close monomer emulsions.
Step 4. prepares ASA latex: PBA base latex obtained in step 2 being added into the reactor equipped with blender
60g, then add into deionized water 150g, potassium peroxydisulfate 1g, stirring, and be warming up to 60 DEG C, continuous dropwise addition mix monomer lotion is even
Speed, which is added dropwise to, to be finished, then is warming up to 90 DEG C, is reacted 4h, is obtained ASA latex；Wherein PBA base latex is with solid meter.
The ASA latex that step 5. obtains step 4 obtains ASA graft copolymerization through demulsification, cohesion, washing, filtering, drying
Object, number A1.
Embodiment 2
The preparation of step 1. organosilicon pre-emulsion: trimethyl triphenyl cyclotrisiloxane 30g, dioxane are added into reactor
Oxygroup siloxanes 0.3g, methacryloxypropyl trimethoxy silane 0.5g, dodecyl sodium sulfate 2g, deionized water
150g, stirring at normal temperature 40min are placed into mulser and are emulsified 5min with the speed strength of 6000r/min, and the pre- cream of organosilicon is made
Liquid；
Deionized water 50g stirring is added in the reactor with blender, and is warming up to 60 DEG C, continuous be added dropwise is matched in advance
The organosilicon pre-emulsion made, is at the uniform velocity added dropwise to and finishes, then is warming up to 90 DEG C, reacts 4h, obtains organic silicon emulsion；
Step 2. prepares PBA base latex: the cream of organosilicon obtained in step 1 being added into the reactor equipped with blender
Liquid 20g, then add into deionized water 100g, dodecyl sodium sulfate 0.3g, potassium peroxydisulfate 1g, stirring, and be warming up to 60 DEG C, even
Continuous dropwise addition is prepared in advance to contain cumyl hydroperoxide 0.5g, butanediol diacrylate 1.5g, Butyl Acrylate Monomer
The mix monomer of 40g, is at the uniform velocity added dropwise to and finishes, then is warming up to 90 DEG C, reacts 4h, obtains PBA base latex；Wherein organosilicon cream
Liquid is with solid meter.
Step 3. prepares mix monomer lotion: cumyl hydroperoxide 0.5g, n- dodecyl mereaptan being added into reactor
0.1g, styrene 10g, acrylonitrile 30g, dodecyl sodium sulfate 0.3g, deionized water 100g, stirring at normal temperature 40min are made mixed
Close monomer emulsions.
Step 4. prepares ASA latex: PBA base latex obtained in step 2 being added into the reactor equipped with blender
60g, then add into deionized water 100g, potassium peroxydisulfate 1g, stirring, and be warming up to 60 DEG C, continuous dropwise addition mix monomer lotion is even
Speed, which is added dropwise to, to be finished, then is warming up to 90 DEG C, is reacted 4h, is obtained ASA latex；Wherein PBA base latex is with solid meter.
The ASA latex that step 5. obtains step 4 obtains ASA graft copolymerization through demulsification, cohesion, washing, filtering, drying
Object, number A2.
Embodiment 3
The preparation of step 1. organosilicon pre-emulsion: trimethyl triphenyl cyclotrisiloxane 30g, dioxane are added into reactor
Oxygroup siloxanes 0.3g, methacryloxypropyl trimethoxy silane 0.5g, dodecyl sodium sulfate 2g, deionized water
150g, stirring at normal temperature 40min are placed into mulser and are emulsified 5min with the speed strength of 6000r/min, and the pre- cream of organosilicon is made
Liquid；
Deionized water 50g stirring is added in the reactor with blender, and is warming up to 60 DEG C, continuous be added dropwise is matched in advance
The organosilicon pre-emulsion made, is at the uniform velocity added dropwise to and finishes, then is warming up to 90 DEG C, reacts 4h, obtains organic silicon emulsion；
Step 2. prepares PBA base latex: the cream of organosilicon obtained in step 1 being added into the reactor equipped with blender
Liquid 30g, then add into deionized water 100g, dodecyl sodium sulfate 0.3g, potassium peroxydisulfate 1g, stirring, and be warming up to 60 DEG C, even
Continuous dropwise addition is prepared in advance to contain cumyl hydroperoxide 0.5g, butanediol diacrylate 1.5g, Butyl Acrylate Monomer
The mix monomer of 30g, is at the uniform velocity added dropwise to and finishes, then is warming up to 90 DEG C, reacts 4h, obtains PBA base latex；Wherein organosilicon cream
Liquid is with solid meter.
Step 3. prepares mix monomer lotion: cumyl hydroperoxide 0.5g, n- dodecyl mereaptan being added into reactor
0.1g, styrene 10g, acrylonitrile 30g, dodecyl sodium sulfate 0.3g, deionized water 100g, stirring at normal temperature 40min are made mixed
Close monomer emulsions.
Step 4. prepares ASA latex: PBA base latex obtained in step 2 being added into the reactor equipped with blender
60g, then add into deionized water 100g, potassium peroxydisulfate 1g, stirring, and be warming up to 60 DEG C, continuous dropwise addition mix monomer lotion is even
Speed, which is added dropwise to, to be finished, then is warming up to 90 DEG C, is reacted 4h, is obtained ASA latex；Wherein PBA base latex is with solid meter.
The ASA latex that step 5. obtains step 4 obtains ASA graft copolymerization through demulsification, cohesion, washing, filtering, drying
Object, number A3.
Embodiment 4
The preparation of step 1. organosilicon pre-emulsion: trimethyl triphenyl cyclotrisiloxane 30g, dioxane are added into reactor
Oxygroup siloxanes 0.3g, methacryloxypropyl trimethoxy silane 0.6g, dodecyl sodium sulfate 2g, deionized water
150g, stirring at normal temperature 30min place into mulser and emulsify 5min with the speed strength of 5000r/min, the pre- cream of organosilicon is made
Liquid；
Deionized water 50g stirring is added in the reactor with blender, and is warming up to 50 DEG C, continuous be added dropwise is matched in advance
The organosilicon pre-emulsion made, is at the uniform velocity added dropwise to and finishes, then is warming up to 80 DEG C, reacts 3h, obtains organic silicon emulsion；
Step 2. prepares PBA base latex: the cream of organosilicon obtained in step 1 being added into the reactor equipped with blender
Liquid 40g, then add into deionized water 150g, dodecyl sodium sulfate 0.3g, potassium peroxydisulfate 1g, stirring, and be warming up to 50 DEG C, even
Continuous dropwise addition is prepared in advance to contain cumyl hydroperoxide 0.5g, butanediol diacrylate 1.5g, acrylic acid ethyl ester monomer
The mix monomer of 20g, is at the uniform velocity added dropwise to and finishes, then is warming up to 80 DEG C, reacts 3h, obtains PBA base latex；Wherein organosilicon cream
Liquid is with solid meter.
Step 3. prepares mix monomer lotion: cumyl hydroperoxide 0.5g, n- dodecyl mereaptan being added into reactor
0.1g, styrene 10g, acrylonitrile 30g, dodecyl sodium sulfate 0.3g, deionized water 100g, stirring at normal temperature 30min are made mixed
Close monomer emulsions.
Step 4. prepares ASA latex: PBA base latex obtained in step 2 being added into the reactor equipped with blender
60g, then add into deionized water 100g, sodium peroxydisulfate 1g, stirring, and be warming up to 50 DEG C, continuous dropwise addition mix monomer lotion is even
Speed, which is added dropwise to, to be finished, then is warming up to 80 DEG C, is reacted 3h, is obtained ASA latex；Wherein PBA base latex is with solid meter.
The ASA latex that step 5. obtains step 4 obtains ASA graft copolymerization through demulsification, cohesion, washing, filtering, drying
Object, number A4.
Embodiment 5
The preparation of step 1. organosilicon pre-emulsion: trimethyl triphenyl cyclotrisiloxane 10g, dioxane are added into reactor
Oxygroup siloxanes 0.1g, silane coupling agent 0.4g, neopelex 1g, deionized water 50g containing acrylate, room temperature
60min is stirred, places into mulser and 10min is emulsified with the speed strength of 10000r/min, organosilicon pre-emulsion is made；
Deionized water 50g stirring is added in the reactor with blender, and is warming up to 60 DEG C, continuous be added dropwise is matched in advance
The organosilicon pre-emulsion made, is at the uniform velocity added dropwise to and finishes, then is warming up to 90 DEG C, reacts 4h, obtains organic silicon emulsion；
Step 2. prepares PBA base latex: the cream of organosilicon obtained in step 1 being added into the reactor equipped with blender
Liquid 10g, then add into deionized water 100g, neopelex 0.1g, potassium peroxydisulfate 0.5g, stirring, and be warming up to 60
DEG C, continuous dropwise addition is prepared different pungent containing cumyl peroxide 0.1g, butanediol diacrylate 0.5g, acrylic acid in advance
The mix monomer of ester monomer 40g, is at the uniform velocity added dropwise to and finishes, then is warming up to 90 DEG C, reacts 4h, obtains PBA base latex；Wherein have
Machine silicon emulsion is with solid meter.
Step 3. prepares mix monomer lotion: cumyl hydroperoxide 0.1g, n- dodecyl mereaptan being added into reactor
0.05g, styrene 10g, acrylonitrile 35g, neopelex 0.1g, deionized water 50g, stirring at normal temperature 60min are made
Mix monomer lotion.
Step 4. prepares ASA latex: PBA base latex obtained in step 2 being added into the reactor equipped with blender
60g, then add into deionized water 100g, potassium peroxydisulfate 0.5g, stirring, and be warming up to 60 DEG C, it is continuous that mix monomer lotion is added dropwise,
It is at the uniform velocity added dropwise to and finishes, then be warming up to 90 DEG C, react 4h, obtain ASA latex；Wherein PBA base latex is with solid meter.
The ASA latex that step 5. obtains step 4 obtains ASA graft copolymerization through demulsification, cohesion, washing, filtering, drying
Object, number A5.
Embodiment 6
The preparation of step 1. organosilicon pre-emulsion: trimethyl triphenyl cyclotrisiloxane 20g, dioxane are added into reactor
Oxygroup siloxanes 1g, methacryloxypropyl 2g, lauryl sodium sulfate 4g, deionized water 100g,
Stirring at normal temperature 45min places into mulser and emulsifies 8min with the speed strength of 7500r/min, organosilicon pre-emulsion is made；
Deionized water 50g stirring is added in the reactor with blender, and is warming up to 55 DEG C, continuous be added dropwise is matched in advance
The organosilicon pre-emulsion made, is at the uniform velocity added dropwise to and finishes, then is warming up to 85 DEG C, reacts 3.5h, obtains organic silicon emulsion；
Step 2. prepares PBA base latex: the cream of organosilicon obtained in step 1 being added into the reactor equipped with blender
Liquid 40g, then add into deionized water 150g, lauryl sodium sulfate 0.5g, potassium peroxydisulfate 2g, stirring, and be warming up to 55 DEG C, even
It is continuous be added dropwise it is prepared in advance containing lauroyl peroxide 1g, hexanediol diacrylate 2.5g, Butyl Acrylate Monomer 10g
Mix monomer is at the uniform velocity added dropwise to and finishes, then is warming up to 90 DEG C, reacts 4h, obtains PBA base latex；Wherein organic silicon emulsion with
Solid meter.
Step 3. prepares mix monomer lotion: cumyl hydroperoxide 1g, n- dodecyl mereaptan being added into reactor
0.25g, styrene 35g, acrylonitrile 15g, lauryl sodium sulfate 0.5g, deionized water 100g, stirring at normal temperature 45min are made
Mix monomer lotion.
Step 4. prepares ASA latex: PBA base latex obtained in step 2 being added into the reactor equipped with blender
50g, then add into deionized water 150g, potassium peroxydisulfate 2g, stirring, and be warming up to 55 DEG C, continuous dropwise addition mix monomer lotion is even
Speed, which is added dropwise to, to be finished, then is warming up to 85 DEG C, is reacted 3.5h, is obtained ASA latex；Wherein PBA base latex is with solid meter.
The ASA latex that step 5. obtains step 4 obtains ASA graft copolymerization through demulsification, cohesion, washing, filtering, drying
Object, number A6.
Embodiment 7
The preparation of step 1. organosilicon pre-emulsion: tetramethyl tetraphenyl cyclotetrasiloxane 15g, dioxane are added into reactor
Oxygroup siloxanes 0.6g, methacryloxypropyl 1.5g, alkylphenol-polyethenoxy base ether 2.5g, go from
Sub- water 120g, stirring at normal temperature 30min place into mulser and emulsify 5min with the speed strength of 5000r/min, organosilicon is made
Pre-emulsion；
Deionized water 50g stirring is added in the reactor with blender, and is warming up to 50 DEG C, continuous be added dropwise is matched in advance
The organosilicon pre-emulsion made, is at the uniform velocity added dropwise to and finishes, then is warming up to 80 DEG C, reacts 3h, obtains organic silicon emulsion；
Step 2. prepares PBA base latex: the cream of organosilicon obtained in step 1 being added into the reactor equipped with blender
Liquid 25g, then add into deionized water 100g, alkylphenol-polyethenoxy base ether 0.2g, potassium peroxydisulfate 1.5g, stirring, and be warming up to
50 DEG C, continuous dropwise addition is prepared in advance to contain peroxidized t-butyl perbenzoate 0.5g, ethylene glycol diacrylate 1.5g, propylene
The mix monomer of acid butyl ester monomer 25g, is at the uniform velocity added dropwise to and finishes, then is warming up to 80 DEG C, reacts 3h, obtains PBA base latex；Its
Middle organic silicon emulsion is with solid meter.
Step 3. prepares mix monomer lotion: cumyl hydroperoxide 0.5g, n- dodecyl mereaptan being added into reactor
0.2g, styrene 10g, acrylonitrile 40g, alkylphenol-polyethenoxy base ether 0.5g, deionized water 150g, stirring at normal temperature 45min, system
Obtain mix monomer lotion.
Step 4. prepares ASA latex: PBA base latex obtained in step 2 being added into the reactor equipped with blender
50g, then add into deionized water 100g, ammonium persulfate 1g, stirring, and be warming up to 50 DEG C, continuous dropwise addition mix monomer lotion is even
Speed, which is added dropwise to, to be finished, then is warming up to 80 DEG C, is reacted 3h, is obtained ASA latex；Wherein PBA base latex is with solid meter.
The ASA latex that step 5. obtains step 4 obtains ASA graft copolymerization through demulsification, cohesion, washing, filtering, drying
Object, number A7.
Comparative example 1
The preparation of step 1. pre-emulsion: into reactor be added butyl acrylate 30g, dodecyl sodium sulfate 2g, go from
Sub- water 150g, stirring at normal temperature 40min are placed into mulser and are emulsified 5min with the speed strength of 6000r/min, and pre-emulsion is made；
Deionized water 50g, stirring are added in the reactor with blender, and is warming up to 60 DEG C, continuous dropwise addition is preparatory
Prepared pre-emulsion, is at the uniform velocity added dropwise to and finishes, then is warming up to 90 DEG C, reacts 4h, obtains acrylic rubber lotion；
Acrylic rubber lotion 20g obtained in step 1 is added into the reactor equipped with blender for step 2., then mends
Deionized water 100g, dodecyl sodium sulfate 0.3g, potassium peroxydisulfate 1g, stirring is added, and is warming up to 60 DEG C, it is continuous to be added dropwise in advance
The prepared mixing list containing cumyl hydroperoxide 0.5g, butanediol diacrylate 1.5g, Butyl Acrylate Monomer 40g
Body is at the uniform velocity added dropwise to and finishes, then is warming up to 90 DEG C, reacts 4h, obtains PBA base latex；Wherein acrylic rubber lotion with
Solid meter.
Step 3. mix monomer lotion: cumyl hydroperoxide 0.5g, n- dodecyl mereaptan 0.1g, benzene are added into reactor
Mix monomer is made in ethylene 10g, acrylonitrile 30g, dodecyl sodium sulfate 0.3g, deionized water 100g, stirring at normal temperature 40min
Lotion.
To equipped with blender reactor in be added step 2 obtained in base latex 60g, then add into metering go from
Sub- water 100g, potassium peroxydisulfate 1g, stirring, and 60 DEG C are warming up to, and it is continuous that mix monomer lotion is added dropwise, it is at the uniform velocity added dropwise to and finishes, then
90 DEG C are warming up to, 4h is reacted, obtains ASA latex；Wherein base latex is with solid meter.
The ASA latex that step 4. obtains step 3 obtains ASA graft copolymerization through demulsification, cohesion, washing, filtering, drying
Object, number B1.
By calculating, heat resistance modified component phenyl siloxane rubber content is respectively 10%, 20% and 30% in A1, A2 and A3.
The ASA copolymer of above-mentioned each example and other resins, addition auxiliary agent are separately added into proportion in high speed ingredient blender, high speed is mixed
It closes 1 minute, obtains premix.Each component ratio is as shown in table 1:
Table 1
Raw materials in the present embodiment are as follows:
1, AS resin: trade mark 138H, Zhenjiang Qi Mei company.
2, PMMA resin: trade mark MF001, melt index 14g/10min (230 DEG C, 3.8kg), Mitsubishi Li Yang company.
3, heat-proof modifier: trade mark MS-NB, Japan Electric chemistry.
4, carbon black: trade mark 660R, Cabot Co., Ltd, the U.S..
Mixed premix is placed in twin-screw and is granulated through melting extrusion, extrusion process are as follows: dual-screw-stem machine temperature
Area: one section of 180 DEG C, two sections of temperature 200 DEG C, three sections of temperature 220 DEG C, four sections of temperature 230 DEG C, five sections of temperature 240 DEG C of temperature, head
240 DEG C of temperature；Host frequency: 35Hz；Feeding frequency: 15Hz；Pelleter revolving speed: 300r/min；By the material cooling of extrusion, make
Grain, obtains corresponding product particles.
Batten preparation and test method:
Particle prepared by the above method is dried into 4h in 80 DEG C of air dry ovens, passes through injection molding test bars.
Izod notch impact strength: ISO 180/1A standard testing, impact energy 2.75J are pressed.
Heat distortion temperature: pressing ISO 75, test condition 1.8MPa, and 120 DEG C/h.
Color difference L value: ISO 7724 is pressed, spectrophotometer test, D65 standard sources, 10 ° of viewing angle includes that mirror surface is anti-
It penetrates.
Glossiness: pressing 2813 standard testing of ISO, and test angle is 20 °.
The comparison of 2 test result of table
It can be obviously improved material thermal resistance by comparing can be seen that physical blending addition heat-proof modifier, but material is tough
Property decline it is obvious, blackness and glossiness are also greatly reduced；It equally includes 9 parts of heat resistance modified components that comparison C3, D2, which can be seen that,
Using phenyl siloxane rubber chemical modification, material thermal resistance promotion is bigger, adds the D2 heat resistance of 9 parts of heat-proof modifiers close to containing 6
The C2 of part phenyl siloxane rubber.C1, C2, C3 impact strength and cosmetic variation are little, and chemical modification influences the physical property of product smaller.
The foregoing is merely illustrative of the preferred embodiments of the present invention, is not intended to limit the invention, all in essence of the invention
Made any modifications, equivalent replacements, and improvements etc., should all be included in the protection scope of the present invention within mind and principle.
All features disclosed in this specification can combine in any way other than mutually exclusive feature.
Any feature disclosed in this specification unless specifically stated can be equivalent or with similar purpose by other
Alternative features are replaced.That is, unless specifically stated, each feature is an example in a series of equivalent or similar characteristics
.
Claims (10)
1. a kind of preparation method of the ASA graft copolymer of chemical modification efficient heat-resisting, which is characterized in that with the phenyl silicon of crosslinking
Rubber latex is seed, and after being coated with acrylic rubber to it, the ASA grafting is made in graft phenylethene, acrylonitrile
Copolymer；Wherein, the phenyl siloxane rubber has acrylate group, and the phenyl siloxane rubber accounts for the ASA graft copolymer
Mass percent be 10%-40%.
2. a kind of preparation method of the ASA graft copolymer of chemical modification efficient heat-resisting, comprising the following steps:
Step 1. prepares organosilicon pre-emulsion: phenyl siloxane monomer being added into reactor, the first crosslinking agent, contains acrylate
The silane coupling agent of base, emulsifier, deionized water emulsify in mulser after stirring and organosilicon pre-emulsion are made,
Deionized water is added in the reactor with blender, stirs, the organosilicon pre-emulsion is continuously added dropwise in heating, drips
It adds complete, then heats up, reaction a period of time, obtain organic silicon emulsion；
Step 2. prepares PBA base latex: organic silicon emulsion made from step 1 is added into the reactor equipped with blender, then
Deionized water, emulsifier, inorganic initiator is added, stirs, heating, continuous be added dropwise is handed over containing organic peroxy initiator, second
The mix monomer for joining agent, acrylate monomer, is added dropwise, then heat up, and reaction a period of time, obtains PBA base latex；
Step 3. prepares mix monomer lotion: organic peroxy initiator, chain-transferring agent, styrene, third being added into reactor
Mix monomer lotion is made in alkene nitrile, emulsifier, deionized water, stirring；
Step 4. prepares ASA latex: PBA base latex made from step 2 being added into the reactor equipped with blender, adds
Deionized water, emulsifier, inorganic initiator stir, heating, and mix monomer lotion made from continuous a dropping step 3 has been added dropwise to
Finish, then heat up, reaction a period of time, obtains ASA latex；
ASA latex made from step 4 through demulsification, cohesion, washing, filtering, drying, is obtained ASA graft copolymer by step 5..
3. a kind of preparation method of the ASA graft copolymer of chemical modification efficient heat-resisting according to claim 2, feature
It is, phenyl siloxane monomer, the first crosslinking agent in the step 1, containing acrylate-based silane coupling agent, emulsifier, water
Weight ratio be 10~30:0.1~1:0.4~2:1~4:50~200.
4. a kind of preparation method of the ASA graft copolymer of chemical modification efficient heat-resisting according to claim 2, feature
It is, organic silicon emulsion, deionized water, emulsifier, inorganic initiator, organic peroxy initiator, second are handed in the step 2
Join agent, the weight ratio of acrylate monomer is 10~40:100~150:0.1~0.5:0.5~2:0.1~1.0:0.5~2.5:
20~50, wherein organic silicon emulsion is with solid meter.
5. a kind of preparation method of the ASA graft copolymer of chemical modification efficient heat-resisting according to claim 2, feature
Be, in the step 3, organic peroxy initiator, chain-transferring agent, styrene, acrylonitrile, emulsifier, deionized water weight
Amount is than being 0.1~1.0:0.05~0.25:10~35:15~40:0.1~0.5:50~150；
In the step 4, PBA base latex, deionized water, the weight ratio of inorganic initiator are 50~60:150~250:0.1
~0.5；Wherein PBA base latex is with solid meter.
6. a kind of preparation method of the ASA graft copolymer of chemical modification efficient heat-resisting according to claim 2, feature
Be, in the step 1, when preparing organosilicon pre-emulsion, prior to after stirring at normal temperature 30-60min in mulser with 5000-
The speed strength emulsification 5-10min of 10000r/min；Deionized water, hydrochloric acid are added in the reactor with blender, stirs,
And it is warming up to 50-60 DEG C, and it is continuous that prepared organosilicon pre-emulsion in advance is added dropwise, it is at the uniform velocity added dropwise to and finishes, then be warming up to 80-90
DEG C, 3-4h is reacted, organic silicon emulsion is obtained.
7. a kind of preparation method of the ASA graft copolymer of chemical modification efficient heat-resisting according to claim 2, feature
It is, in the step 2, organic silicon emulsion made from step 1 is added into the reactor equipped with blender, adds deionization
Water, emulsifier, inorganic initiator, stirring, are warming up to 50-60 DEG C, the mix monomer are continuously added dropwise, after being at the uniform velocity added dropwise,
It is warming up to 80-90 DEG C again, reacts 3-4h, obtains PBA base latex.
8. a kind of preparation method of the ASA graft copolymer of chemical modification efficient heat-resisting according to claim 2, feature
It is, in the step 3, the condition of stirring is stirring at normal temperature 30-60min；
Or/and in the step 4, PBA base latex made from step 2 is added into the reactor equipped with blender, adds
Deionized water, emulsifier, inorganic initiator, stirring are warming up to 50-60 DEG C, the cream of mix monomer made from continuous a dropping step 3
Liquid is at the uniform velocity added dropwise to and finishes, then is warming up to 80-90 DEG C, reacts 3-4h, obtains ASA latex.
9. a kind of preparation of the ASA graft copolymer of chemical modification efficient heat-resisting according to claim 2-8 any one
Method, which is characterized in that the phenyl siloxane monomer is the siloxanes ring body containing phenyl；
Or/and first crosslinking agent is containing the siloxanyl monomers for being more than or equal to two alkoxies；
Or/and it is described containing acrylate-based silane coupling agent be methacryloxypropyl trimethoxy silane, methyl-prop
Any one or a few in alkene acryloxypropylethoxysilane triethoxysilane；
Or/and any one of the acrylate monomer in ethyl acrylate, butyl acrylate or Isooctyl acrylate monomer
Or it is several；
Or/and the emulsifier is selected from neopelex, lauryl sodium sulfate, dodecyl sodium sulfate, alkyl phenol
The mixture of one or more of polyoxyethylene ether；
Or/and the organic peroxide evocating agent is selected from cumyl hydroperoxide, cumyl peroxide, peroxidating laurel
Any one or a few in acyl, peroxidized t-butyl perbenzoate；
Or/and second crosslinking agent is selected from ethylene glycol diacrylate, butanediol diacrylate, diacrylate hexylene glycol
Ester, in any one or a few；
Or/and the inorganic initiator is one or more of in ammonium persulfate, potassium peroxydisulfate, sodium peroxydisulfate；
Or/and any one or a few in n- dodecyl mereaptan, tert-dodecyl mercaptan, n-octyl mercaptan of the chain-transferring agent.
10. using ASA graft copolymer made from preparation method described in any one of claim 1-9.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201811617117.9A CN109666102B (en) | 2018-12-28 | 2018-12-28 | A kind of the ASA graft copolymer and preparation method of chemical modification efficient heat-resisting |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201811617117.9A CN109666102B (en) | 2018-12-28 | 2018-12-28 | A kind of the ASA graft copolymer and preparation method of chemical modification efficient heat-resisting |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN109666102A CN109666102A (en) | 2019-04-23 |
| CN109666102B true CN109666102B (en) | 2019-11-05 |
Family
ID=66146429
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201811617117.9A Active CN109666102B (en) | 2018-12-28 | 2018-12-28 | A kind of the ASA graft copolymer and preparation method of chemical modification efficient heat-resisting |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN109666102B (en) |
Families Citing this family (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111393576B (en) * | 2020-03-06 | 2020-11-03 | 四川中物材料股份有限公司 | Toughening agent with flame retardant effect, and synthesis method and application thereof |
| CN111471146B (en) * | 2020-05-15 | 2021-10-22 | 华陆工程科技有限责任公司 | High-performance ASA (acrylonitrile styrene acrylate) graft copolymer and preparation method thereof |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1065664A (en) * | 1991-03-29 | 1992-10-28 | 三菱丽阳株式会社 | The preparation method who contains the graft copolymer particles of rubber |
| CN101175781A (en) * | 2005-05-13 | 2008-05-07 | 株式会社钟化 | Polyorganosiloxane-containing graft copolymer and vinyl chloride resin compositions containing the copolymer |
| CN104693334A (en) * | 2013-12-04 | 2015-06-10 | 三星Sdi株式会社 | Styrene-based copolymer and thermoplastic resin composition including the same |
-
2018
- 2018-12-28 CN CN201811617117.9A patent/CN109666102B/en active Active
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1065664A (en) * | 1991-03-29 | 1992-10-28 | 三菱丽阳株式会社 | The preparation method who contains the graft copolymer particles of rubber |
| CN101175781A (en) * | 2005-05-13 | 2008-05-07 | 株式会社钟化 | Polyorganosiloxane-containing graft copolymer and vinyl chloride resin compositions containing the copolymer |
| CN104693334A (en) * | 2013-12-04 | 2015-06-10 | 三星Sdi株式会社 | Styrene-based copolymer and thermoplastic resin composition including the same |
Also Published As
| Publication number | Publication date |
|---|---|
| CN109666102A (en) | 2019-04-23 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN101575398B (en) | Organosilicon-modified acrylate emulsion and preparation method of coating agent for powder-free gloves | |
| CN102782039B (en) | Thermoplastic resin composition for vehicle lamp housings | |
| JP5845993B2 (en) | Acrylic rubber-based graft copolymer and thermoplastic resin composition | |
| CN109666102B (en) | A kind of the ASA graft copolymer and preparation method of chemical modification efficient heat-resisting | |
| CN101781390B (en) | Preparation method of nuclear shell structure high-silicon silicone acrylic emulsion used for building exterior wall | |
| WO1999006457A1 (en) | Graft copolymer particles and thermoplastic resin compositions | |
| CN1340566A (en) | Multiple polymer additive system and its composition, method and product | |
| CN104292399B (en) | A kind of synthetic method of high-impact PVC modifier | |
| CN100494232C (en) | Method for synthesizing phenylethene /acrylonitrile/ N-phenyl maleimide terpolymer by one-step method | |
| CN100372874C (en) | Chlorinated polyethylene with high maximum elongation, and preparation process and application thereof | |
| CN105348455A (en) | Modified epoxy group acrylic acid matting resin and preparing method | |
| CN101235245B (en) | Method for preparing silicone-acrylate dope | |
| CN1192755A (en) | Polymer compositions for graft copolymers as well as mixtures thereof and thermoplastic compounds contg. same | |
| CN105733120B (en) | A kind of high flowing, high-impact ABS resin and preparation method thereof | |
| CN101137722B (en) | Polymeric lubricant having multi layer structure | |
| CN108948254A (en) | A kind of feature of environmental protection acrylic resin and preparation method thereof | |
| CN107163542A (en) | A kind of PC/AS/ acrylic resins alloy material and preparation method thereof | |
| CN1340567A (en) | Functional liquid-solid additive system: composition method and its product | |
| JP3218192B2 (en) | Flame retardant resin composition | |
| CN107641468A (en) | A kind of water proof fire retardant powdery paints and preparation method thereof | |
| JPH1095911A (en) | Thermoplastic resin composition | |
| CN106280205A (en) | A kind of heat-proof ABS compositions and preparation method thereof | |
| JP3945861B2 (en) | Thermoplastic resin composition | |
| JP2000204220A (en) | Modifier for methacrylic resin | |
| JP3533002B2 (en) | Thermoplastic resin composition |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |