CN109181281A - A kind of alloy toughener for toughening nylon - Google Patents
A kind of alloy toughener for toughening nylon Download PDFInfo
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- CN109181281A CN109181281A CN201810804369.6A CN201810804369A CN109181281A CN 109181281 A CN109181281 A CN 109181281A CN 201810804369 A CN201810804369 A CN 201810804369A CN 109181281 A CN109181281 A CN 109181281A
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- C08F255/00—Macromolecular compounds obtained by polymerising monomers on to polymers of hydrocarbons as defined in group C08F10/00
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- C08F255/02—Macromolecular compounds obtained by polymerising monomers on to polymers of hydrocarbons as defined in group C08F10/00 on to polymers of olefins having two or three carbon atoms
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- C08F255/00—Macromolecular compounds obtained by polymerising monomers on to polymers of hydrocarbons as defined in group C08F10/00
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- C08F255/06—Macromolecular compounds obtained by polymerising monomers on to polymers of hydrocarbons as defined in group C08F10/00 on to polymers of olefins having two or three carbon atoms on to ethene-propene-diene terpolymers
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Abstract
The present invention relates to toughener technical fields, more particularly to a kind of alloy toughener for toughening nylon, by polyolefins thermoplastic elastomer, styrene analog thermoplastic elastomer, first grafted monomers, second grafted monomers, initiator and diluent are made, wherein polyolefins thermoplastic elastomer is the pungent dilute copolymer of ethylene-, ethylene-butene copolymer, bibasic ethylene propylene rubber and the one or more mixtures of ethylene propylene diene rubber, styrene analog thermoplastic elastomer is Styrene-Butadiene-Styrene Block Copolymer, polystyrene-poly (Ethylene/Butylene)-polystyrene block copolymer, one of styrene-isoprene-styrene block copolymer and polystyrene-poly (ethylene-propylene)-polystyrene block copolymer or a variety of mixtures, gained alloy toughener can be suitable for the situation of rigidity keeping nylon Under effectively increase the toughness of nylon, it is good to the synthesis toughening modifying effect of nylon, and preparation process is simple, it is easy to operate.
Description
Technical field
The present invention relates to toughener technical fields, and in particular to a kind of alloy toughener for toughening nylon.
Background technique
Nylon is being commonly called as Fypro, is important engineering plastics, has rigidity big, and creep is small, high mechanical strength,
The advantages that heat-resist, is widely used in the industries such as electric, automobile, building, office equipment, machinery, aerospace, is
To mould the good selection of the metals such as Dai Gang, iron, copper, it is suitable for production wear part, drive mechanism part, household appliance components, vapour
Vehicle manufactures part, chemical machinery part, chemical industry equipment etc..But often limited its application since the toughness of nylon is poor,
It is general in the prior art to carry out toughening by the way that inorganic filler is added, but the effect of toughening is not ideal enough, also there is addition high density
The elastomers such as polyethylene carry out toughening modifying, but while will lead to the hot rising of nylon, rigidity decline is obvious.
Summary of the invention
For the problem that nylon toughness is poor, the purpose of the present invention is to provide a kind of alloy toughenings for toughening nylon
The toughness of nylon can be improved in agent, and the effect of toughening is obvious, while keeping nylon is suitable for rigidity, meets nylon multipurpose application
It is required that.
The present invention provides the following technical solution:
A kind of alloy toughener for toughening nylon, the alloy toughener are made of the components of following parts: polyolefin
50~95 parts of analog thermoplastic elastomer, 5~50 parts of styrene analog thermoplastic elastomer, 0.5~8 part of the first grafted monomers, second
0.1~8 part of grafted monomers, 0.01~0.6 part of initiator and 0.1~1 part of diluent.
As a preference of the present invention, the polyolefins thermoplastic elastomer is the pungent dilute copolymer of ethylene-, Ethylene/Butylene
Copolymer, bibasic ethylene propylene rubber and the one or more mixtures of ethylene propylene diene rubber.
As a preference of the present invention, the styrene analog thermoplastic elastomer is total for s-B-S block
Polymers, polystyrene-poly (Ethylene/Butylene)-polystyrene block copolymer, styrene-isoprene-phenylethene block copolymerization
One of object and polystyrene-poly (ethylene-propylene)-polystyrene block copolymer or a variety of mixtures.
As a preference of the present invention, first grafted monomers are maleic anhydride, maleic acid, anti-butylene two
One of acid, acrylic acid and phthalic anhydride or a variety of mixtures.
As a preference of the present invention, second grafted monomers are styrene, pyridine, caprolactam, methacrylic acid contracting
One of water glyceride and methyl styrene or a variety of mixtures.
As a preference of the present invention, the initiator is that 2,5- dimethyl -2,5 bis- (t-butyl peroxies) changes hexane, 1,
1- (double tert-butyl peroxides) 3,3,5- trimethyl-cyclohexane, cumyl peroxide, dibenzoyl peroxide, bis- (tertiary fourths of 2-
Base isopropyl peroxide) benzene, t-butylcumylperoxide, di-tert-butyl peroxide, benzylhydroperoxide tert-pentyl ester, 2,2- be bis-
(t-amyl peroxy)-butane, two t-amyl peroxy compounds, tert butyl peroxy benzoate, tert-butyl hydroperoxide -2- ethyl hexyl
One of acid esters, tert-butyl hydroperoxide -3,5,5 Trimethylhexanoic acid ester, dibenzoyl peroxide or a variety of mixtures.
As a preference of the present invention, the diluent is acetone, one or more mixing in butanone, ethyl alcohol, ethyl acetate
Object.
Alloy toughener of the invention is maleic anhydride, maleic acid, fumaric acid, acrylic acid or adjacent benzene two
Formic anhydride graft polyolefin analog thermoplastic elastomer and maleic anhydride, maleic acid, fumaric acid, acrylic acid or neighbour
The alloy of phthalate anhydride graft phenylethene analog thermoplastic elastomer, wherein polyolefins thermoplastic elastomer includes that ethylene-is pungent
One of dilute copolymer, ethylene-butene copolymer, bibasic ethylene propylene rubber and ethylene propylene diene rubber are a variety of, phenylethylene heat
Thermoplastic elastic includes Styrene-Butadiene-Styrene Block Copolymer, polystyrene-poly (Ethylene/Butylene)-polystyrene
Block copolymer, styrene-isoprene-styrene block copolymer and polystyrene-poly (ethylene-propylene)-polystyrene
One of block copolymer is a variety of.Since the flexibility of polyolefins thermoplastic elastomer is big, by polyolefins thermoplastic bullet
Property body be separately added in nylon as toughener in use, the thermoplasticity that will lead to nylon rise, rigidity decline it is obvious, influence
Properties of nylons；On the other hand polyolefins thermoplastic body and organic rigid-particle such as polystyrene thermoplastic are used in mixed way
When both be easy to appear layering, can not play the role of collaboration enhancing；And the soft segment in polyolefins thermoplastic elastomer
Ratio is little, causes molecule based on rigid radical, although therefore be separately added in nylon that toughness can be improved,
Toughening effect is poor, and application requirement is not achieved.And present inventor has found by long term test, by polyolefins thermoplastic body
It is mixed to form alloy use according to a certain mass ratio with styrene hydrocarbon thermoplastic elastomer to be added in nylon, is keeping preferable
Make the rigidity of nylon suitable while toughening effect.Inventor thinks since there are rubber in styrene hydrocarbon thermoplastic's elastomer
It is high to make the compatibility of polyolefins thermoplastic elastomers and styrene hydrocarbon thermoplastic elastomer for phase flexible portion, and in alloy
Rubber phase in flexible polyolefins thermoplastic elastomer and polystyrene-type thermoplastic elastomers can be used as toughening body
The toughening main body of system assigns nylon toughness, and the polystyrene Duan Ze in polystyrene-type thermoplastic elastomers is as organic rigid
Particle plays the role of coordination plasticizing in toughened system, to reach comprehensive toughening effect.In addition, in the first grafted monomers
Acid anhydrides or carboxyl are grafted to the polyethylene fraction of thermoplastic elastomer (TPE), by with the amide groups increased response thermoplastic elastomehc in nylon
Property body compatibility enhance the toughening effect of alloy toughener to enhance the toughness of nylon.
The preparation method of the above-mentioned alloy toughener for toughening nylon, comprising the following steps:
(1) by polyolefins thermoplastic elastomer, styrene analog thermoplastic elastomer, the first grafted monomers, the second grafted monomers,
Initiator and diluent are uniformly mixed, and obtain primary material；
(2) primary material is sent into extruding pelletization in extruder, it is then cooling, be dried to obtain alloy toughening for toughening nylon
Agent.
As the preferred of the method for the present invention, first by initiator, diluent, the first grafted monomers and second in step (1)
Grafted monomers are sequentially added in styrene analog thermoplastic elastomer and are stirred evenly, and then add polyolefins thermoplastic elastomer
Obtain primary material.
As the preferred of the method for the present invention, extruder used is double screw extruder, 1st area of extruder to 12 in step (2)
Area's temperature setting be 80 DEG C, 150 DEG C, 180 DEG C, 195 DEG C, 195 DEG C, 195 DEG C, 195 DEG C, 195 DEG C, 180 DEG C, 170 DEG C, 160 DEG C,
150 DEG C, head is 170 DEG C.
Alloy toughener of the invention is prepared by way of mixing, extruding pelletization, and simple process is easy to operate, wherein
Since the density of thermoplastic polystyrene elastomer is relatively small, directly mixing with polyolefins thermoplastic elastomer will appear point
Phenomena such as layer, uneven mixing, therefore first by liquid such as initiator, diluent, the first grafted monomers and the second grafted monomers
Raw material is mixed with thermoplastic polystyrene elastomer, so that thermoplastic polystyrene elastomer is fully absorbed rear density and is increased, then with
Polyolefins thermoplastic elastomer mixing, is uniformly mixed, is not in lamination.
Beneficial effects of the present invention are as follows:
Alloy toughener for toughening nylon of the invention is by polyolefins thermoplastic elastomer and polystyrene-type thermoplastic
Elastomer is blended to be granulated and be made under the graft modification effect of the first grafted monomers, can be suitable for the situation of rigidity keeping nylon
Under effectively increase the toughness of nylon, it is good to the synthesis toughening modifying effect of nylon, and the preparation process of extruding pelletization is simple, behaviour
Facilitate.
Specific embodiment
A specific embodiment of the invention is described further below.
Unless otherwise instructed, raw material employed in the present invention is commercially available or commonly used in the art, such as
Without special instruction, the method in following embodiments is the conventional method of this field.
Alloy toughener of the invention is made through following methods
(1) initiator, diluent, the first grafted monomers and the second grafted monomers are first sequentially added into polystyrene-type thermoplastic bullet
Property body in stir evenly, then add polyolefins thermoplastic elastomer be uniformly mixed obtain primary material；
(2) primary material is sent into extruding pelletization in double screw extruder, 1st area of double screw extruder to 12 area's temperature settings is 80
DEG C, 150 DEG C, 180 DEG C, 195 DEG C, 195 DEG C, 195 DEG C, 195 DEG C, 195 DEG C, 180 DEG C, 170 DEG C, 160 DEG C, 150 DEG C, head is
It is 170 DEG C, then cooling, be dried to obtain alloy toughener for toughening nylon.
Shown in group prejudice following embodiment using the alloy toughener of above method preparation.
Embodiment 1
A kind of alloy toughener for toughening nylon, alloy toughener are made of following component: the pungent dilute copolymer 50g of ethylene-,
Styrene-Butadiene-Styrene Block Copolymer 5g, maleic anhydride 0.5g, the second grafted monomers be styrene 0.1g, 2,
5- dimethyl -2,5 bis- (t-butyl peroxies) changes hexane 0.01g and acetone 0.1g.
Embodiment 2
A kind of alloy toughener for toughening nylon, alloy toughener are made of following component: ethylene-butene copolymer 55g,
Polystyrene-poly (Ethylene/Butylene)-polystyrene block copolymer 10g, maleic acid 0.55g, pyridine 0.5g, 1,1- are (double
Tert-butyl peroxide) 3,3,5- trimethyl-cyclohexane 0.05g and butanone 0.2g.
Embodiment 3
A kind of alloy toughener for toughening nylon, alloy toughener are made of following component: bibasic ethylene propylene rubber 60g, benzene
Ethylene-isoprene-styrene block copolymer 15g, fumaric acid 1.5g, caprolactam 1.0g, cumyl peroxide
0.1g and ethyl alcohol 0.3g.
Embodiment 4
A kind of alloy toughener for toughening nylon, alloy toughener are made of following component: ethylene propylene diene rubber 65g, gathering
Poly- (the ethylene-propylene)-polystyrene block copolymer 20g of styrene-, acrylic acid 2.0g, glycidyl methacrylate
1.5g, dibenzoyl peroxide 0.15g and ethyl acetate 0.4g.
Embodiment 5
A kind of alloy toughener for toughening nylon, alloy toughener are made of following component: the pungent dilute copolymer of ethylene-, second
Alkene-butylene copolymer 70g, polystyrene-poly (ethylene-propylene)-polystyrene block copolymer 25g, phthalic anhydride
2.5g, methyl styrene 2.0g, bis- (2- t-butylperoxyisopropyl) benzene 0.2g and ethyl acetate 0.5g.
Embodiment 6
A kind of alloy toughener for toughening nylon, alloy toughener are made of following component: bibasic ethylene propylene rubber and ternary
EP rubbers 75g, polystyrene-poly (ethylene-propylene)-polystyrene block copolymer 30g, phthalic anhydride 3.0g, first
Base styrene 2.5g, t-butylcumylperoxide 0.25g and ethyl acetate 0.6g.
Embodiment 7
A kind of alloy toughener for toughening nylon, alloy toughener are made of following component: the pungent dilute copolymer of ethylene-, two
First EP rubbers 80g, Styrene-Butadiene-Styrene Block Copolymer, polystyrene-poly (ethylene-propylene)-polystyrene
Block copolymer 35g, phthalic anhydride 3.5g, methyl styrene 3.0g, di-tert-butyl peroxide 0.3g and ethyl acetate
0.7g。
Embodiment 8
A kind of alloy toughener for toughening nylon, alloy toughener are made of following component: the pungent dilute copolymer of ethylene-, second
Alkene-butylene copolymer, ethylene propylene diene rubber 85g, Styrene-Butadiene-Styrene Block Copolymer, polystyrene-poly (second
Alkene-butylene)-polystyrene block copolymer, polystyrene-poly (ethylene-propylene)-polystyrene block copolymer 40g, adjacent benzene
Dicarboxylic acid anhydride 4.0g, methyl styrene 3.5g, benzylhydroperoxide tert-pentyl ester 0.35g and acetone 0.8g.
Embodiment 9
A kind of alloy toughener for toughening nylon, alloy toughener are made of following component: ethylene-butene copolymer, two
First EP rubbers and ethylene propylene diene rubber 90g, styrene-isoprene-styrene block copolymer and polystyrene-poly (second
Alkene-propylene)-polystyrene block copolymer 45g, phthalic anhydride 5g, bis- (the tertiary pentyl mistakes of methyl styrene 5g, 2,2-
Oxygen)-butane 0.45g and acetone 0.9g.
Embodiment 10
A kind of alloy toughener for toughening nylon, alloy toughener are made of following component: the pungent dilute copolymer 95g of ethylene-,
Styrene-Butadiene-Styrene Block Copolymer, polystyrene-poly (Ethylene/Butylene)-polystyrene block copolymer, polyphenyl
Poly- (the ethylene-propylene)-polystyrene block copolymer 50g of ethylene-, phthalic anhydride 6g, methyl styrene 6g, two tertiary pentyls
Peroxide 0.5g and ethyl acetate 1g.
Embodiment 11
A kind of alloy toughener for toughening nylon, alloy toughener are made of following component: the pungent dilute copolymer 85g of ethylene-,
Styrene-Butadiene-Styrene Block Copolymer, styrene-isoprene-styrene block copolymer and polystyrene-poly
(ethylene-propylene)-polystyrene block copolymer 35, phthalic anhydride 7g, methyl styrene 7g, tert-butyl hydroperoxide benzene first
Acid esters 0.55g and ethyl acetate 0.8g.
Embodiment 12
A kind of alloy toughener for toughening nylon, alloy toughener are made of following component: the pungent dilute copolymer 95g of ethylene-,
Polystyrene-poly (Ethylene/Butylene)-polystyrene block copolymer, styrene-isoprene-styrene block copolymer and
Polystyrene-poly (ethylene-propylene)-polystyrene block copolymer 40g, phthalic anhydride 8g, methyl styrene 8g, tertiary fourth
Base peroxidating -2 ethyl hexanoic acid ester 0.6g and ethyl acetate 1g.
Embodiment 13
A kind of alloy toughener for toughening nylon, alloy toughener are made of following component: ethylene-butene copolymer 75g,
Styrene-Butadiene-Styrene Block Copolymer, polystyrene-poly (Ethylene/Butylene)-polystyrene block copolymer, benzene second
Alkene-isoprene-styrene block copolymer and polystyrene-poly (ethylene-propylene)-polystyrene block copolymer 25g, neighbour
Phthalate anhydride 4.5g, methyl styrene 6g, tert-butyl hydroperoxide -3,5,5 Trimethylhexanoic acid ester 0.4g and ethyl acetate
0.6g。
Comparative example 1: ethylene-octene copolymer POE resin (DOW, ENGAGE 8150) 100g, maleic anhydride are weighed
2g, cumyl peroxide 0.1g, acetone 1g and white oil 0.2g are blended 20 minutes in low-speed mixer, are added to twin-screw and squeeze
Out in machine, 1st area of extruder to 12 area's temperature settings is 80 DEG C, 150 DEG C, 180 DEG C, 195 DEG C, 195 DEG C, 195 DEG C, 195 DEG C, 195
DEG C, 180 DEG C, 170 DEG C, 160 DEG C, 150 DEG C, head be 170 DEG C, mixed material through fusion plastification, kneading mixing, head extrusion,
Tie rod, cooling, pelletizing and it is dried to obtain polyolefins thermoplastic elastomer toughener.
Comparative example 2 (TPS): weigh polystyrene-poly (Ethylene/Butylene)-polystyrene block copolymer (Yueyang petrochemical industry,
YH501) 100g, maleic anhydride 2g, cumyl peroxide 0.1g, acetone 1g and white oil 0.2g are total in low-speed mixer
It is 20 minutes mixed, it is added in double screw extruder, 1st area of extruder to 12 area's temperature settings is 80 DEG C, 150 DEG C, 180 DEG C, 195
DEG C, 195 DEG C, 195 DEG C, 195 DEG C, 195 DEG C, 180 DEG C, 170 DEG C, 160 DEG C, 150 DEG C, head be 170 DEG C, mixed material is through melting
Plasticizing, kneading mixing, head extrusion, tie rod, cooling, pelletizing and it is dried to obtain styrene analog thermoplastic elastomer toughener.
Performance test
The toughener in PA6 (Ube, 1013B) in addition embodiment 1~13 and comparative example 1~2, toughener add respectively
Adding ratio is 15wt%, and the PA6 of toughening modifying is made, tests the PA6 of more toughening modifyings, and wherein testing standard is such as
Under: tensile strength, elongation at break: ISO527；
Bending strength, bending modulus: ISO178；
IZOD notch impact strength: ISO180；
Test result is shown in Table 1.
1 test result of table
Claims (10)
1. a kind of alloy toughener for toughening nylon, which is characterized in that the alloy toughener by following parts by weight group
Part is made: 50 ~ 95 parts of polyolefins thermoplastic elastomer, 5 ~ 50 parts of styrene analog thermoplastic elastomer, the first grafted monomers 0.5
~8 parts, the second grafted monomers: 0.1~8 part, 0.01~0.6 part of initiator and 0.1~1 part of diluent.
2. alloy toughener according to claim 1, which is characterized in that the polyolefins thermoplastic elastomer is second
The pungent dilute copolymer of alkene-, ethylene-butene copolymer, bibasic ethylene propylene rubber and the one or more mixtures of ethylene propylene diene rubber.
3. alloy toughener according to claim 1, which is characterized in that the styrene analog thermoplastic elastomer is benzene second
Alkene-butadiene-styrene block copolymer, polystyrene-poly (Ethylene/Butylene)-polystyrene block copolymer, styrene-
One of isoprene-styrene block copolymer and polystyrene-poly (ethylene-propylene)-polystyrene block copolymer
Or a variety of mixtures.
4. alloy toughener according to claim 1 or 2 or 3, which is characterized in that first grafted monomers are along fourth
One of enedioic acid acid anhydride, maleic acid, fumaric acid, acrylic acid and phthalic anhydride or a variety of mixtures.
5. alloy toughener according to claim 1 or 2 or 3, which is characterized in that second grafted monomers are benzene second
One of alkene, pyridine, caprolactam, glycidyl methacrylate and methyl styrene or a variety of mixtures.
6. alloy toughener according to claim 1 or 2 or 3, which is characterized in that the initiator is 2,5- diformazan
Base -2,5 bis- (t-butyl peroxies) changes hexane, the bis- tert-butyl peroxides of 1,1-() 3,3,5- trimethyl-cyclohexane, peroxidating
Diisopropylbenzene (DIPB), dibenzoyl peroxide, bis- (2- t-butylperoxyisopropyl) benzene, t-butylcumylperoxide, two tertiary fourths
Bis- (the t-amyl peroxy)-butane of base peroxide, benzylhydroperoxide tert-pentyl ester, 2,2-, two t-amyl peroxy compounds, tert-butyl mistake
Aoxidize benzoic ether, tert-butyl hydroperoxide -2 ethyl hexanoic acid ester, tert-butyl hydroperoxide -3,5,5 Trimethylhexanoic acid ester, hexichol
One of formoxyl peroxide or a variety of mixtures.
7. alloy toughener according to claim 1 or 2 or 3, which is characterized in that the diluent is acetone, butanone, second
One of alcohol, ethyl acetate or a variety of mixtures.
8. the preparation method of the alloy toughener for toughening nylon as described in claim 1 to 7 is any, including following step
It is rapid:
(1) by polyolefins thermoplastic elastomer, styrene analog thermoplastic elastomer, the first grafted monomers, the second grafted monomers,
Initiator and diluent are uniformly mixed, and obtain primary material；
(2) primary material is sent into extruding pelletization in extruder, it is then cooling, be dried to obtain alloy toughening for toughening nylon
Agent.
9. preparation method according to claim 8, which is characterized in that in step (1) first by initiator, diluent,
One grafted monomers and the second grafted monomers are sequentially added in styrene analog thermoplastic elastomer and are stirred evenly, and then add polyene
Hydrocarbon thermoplastic's elastomer obtains primary material.
10. preparation method according to claim 8 or claim 9, which is characterized in that extruder used is twin-screw in step (2)
Extruder, 1st area of extruder to 12 area's temperature settings are 80 DEG C, 150 DEG C, 180 DEG C, 195 DEG C, 195 DEG C, 195 DEG C, 195 DEG C, 195
DEG C, 180 DEG C, 170 DEG C, 160 DEG C, 150 DEG C, head be 170 DEG C.
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| Application Number | Priority Date | Filing Date | Title |
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| CN201810804369.6A CN109181281B (en) | 2018-07-20 | 2018-07-20 | Alloy toughening agent for nylon toughening |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201810804369.6A CN109181281B (en) | 2018-07-20 | 2018-07-20 | Alloy toughening agent for nylon toughening |
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| CN111073202A (en) * | 2019-12-20 | 2020-04-28 | 东莞海丽化学材料有限公司 | Low-temperature-resistant polyolefin modified toughening material, preparation method thereof and nylon material |
| CN111116828A (en) * | 2019-11-29 | 2020-05-08 | 东莞海丽化学材料有限公司 | Ethylene propylene diene monomer copolymer toughening material for nylon, preparation method thereof and nylon material |
| CN114395090A (en) * | 2022-02-18 | 2022-04-26 | 海信（山东）冰箱有限公司 | SBS-g-PS material, preparation method thereof and application thereof in low-temperature toughening modification of PP |
| CN114773767A (en) * | 2022-05-13 | 2022-07-22 | 安徽雄亚塑胶科技有限公司 | Matte dry high-elasticity TPE tension sheet material and preparation method thereof |
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