CN109810457A - A kind of plexiglass/butadiene graft polymer composition and preparation method thereof - Google Patents
A kind of plexiglass/butadiene graft polymer composition and preparation method thereof Download PDFInfo
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Abstract
The invention discloses a kind of plexiglass/butadiene graft polymer compositions, including 100 parts by weight of plexiglass and butadiene graft polymer 35-210 parts by weight, and coordinate the compatibility and optical property matching of plexiglass and butadiene graft polymer by styrene-based polymer, to obtain the product for having both transparent, anti-scratch, shock resistance and excellent machinability.The preparation method of the composition is that polymethyl methacrylate and styrene-based polymer are first carried out mixing granulation, is then kneaded, is melted with butadiene graft polymer again, squeezed out pelletizing and obtain product.
Description
Technical field
The invention belongs to field of resin modification, and more specifically the present invention relates to a kind of plexiglass/fourths
Diene graft polymerization compositions and preparation method thereof.
Background technique
Polymethyl methacrylate (PMMA) has high scratch resistance (pencil hardness is up to 3-5H), weather resistance
Good, also excellent with excellent apparent property, tinctorial property, high transparency has been widely used in daily life.But
It is that PMMA is limited its application there is also the defect of poor toughness.
Butadiene graft polymer such as butadiene-styrene-acrylonitrile polymer (ABS) has excellent comprehensive
Can, it is widely used in the fields such as automobile, electronic apparatus, office appliance, but scratch-resistant, weatherability be not poor, opaque for its presence
Defect.With going deep into for environmentally friendly concept, the product for exempting from spraying obtains client and more and more pays close attention to, this property to basis material
More stringent requirements are proposed for energy, usually requires that the pencil hardness of product reaches F even H or more, this is common butadiene graft
Polymer such as ABS is unapproachable.
Blending and modifying is one of the main path for improving material property, and PMMA/ABS has had both scratch-resistant, high glaze, impact
Improvement and the molding comprehensive performance of easy processing, dyeing product is because have unique visual effect by favor, in household electric
Device, electronic product casing etc. are very widely used.In recent years, some modifying plastics factories are proposed functionalization one after another both at home and abroad
PMMA/ABS alloy material, such as the XG series of LG, SF, BF series of the first woolens of Samsung, the beautiful HAM product in bright and beautiful lake day.Patent
In about PMMA/ABS research it is also very much, as CN200810203577 describes a kind of PMMA/ABS composite material, the material
With good glossiness, higher impact strength and pencil hardness, can be used in white goods industry to gloss and scratch-resistant
In the product having higher requirements；CN201110006556 discloses a kind of antistatic PMMA/ABS alloy, and surface resistivity can
Up to 1.0X108~11Ωm；CN201210072082 improves the flame retardant property of PMMA/ABS alloy product by the way that fire retardant is added
Deng.
In recent years, with the great variety of industry development and Diversity of Product Design, color diversity and transparent design
Many concerns are caused, the variation of design requires the variation of raw material.Due to PMMA and ABS be partially compatible system, and PMMA and
ABS index of refraction difference is larger, so that the product obtained after PMMA and ABS alloy is often nontransparent.
Summary of the invention
In view of above-mentioned the problems of the prior art, the present invention provides a kind of plexiglass/butadiene
Graft polymerization compositions and preparation method thereof.
The object of the present invention is to provide a kind of transparency, Scratch Resistance, shock resistance and excellent machinabilities of having both
Resin combination product.
In order to achieve the above object, the present invention is achieved through the following technical solutions:
The present invention provides a kind of plexiglass/butadiene graft polymer compositions, by weight,
Include following components:
(a) 100 parts of poly- methyl esters methacrylate resin
(b) butadiene graft polymer 40-200 parts,
It is preferred that 50-180 parts, it is 60-150 parts more preferable
The plexiglass and the mutual index of refraction difference of butadiene graft polymer is 0-
0.03, preferably 0-0.01.
Preferably, the index of refraction of the plexiglass is 1.49-1.55.
Preferably, the plexiglass is 50-95 parts by weight, the preferably poly- first of 60-90 parts by weight
Base methyl acrylate and 5-50 parts by weight, the preferably blend of 10-40 parts by weight of styrene based polyalcohol, it is poly- by 100 parts by weight
Polymethyl methacrylate resin poidometer.
The polymethyl methacrylate preferably has a pencil hardness of 3-5H, the measurement of pencil hardness according to
ASTMD3363 (750g) is measured.Polymethyl methacrylate is usually poly- by the inclusion of the mixture of methyl methacrylate
It closes, 60 weight %, the preferably at least methyl methacrylate of 80 weight % is included at least in these mixtures.It is used to prepare
The mixture of polymethyl methacrylate may include with other (methyl) acrylate of methyl methacrylate copolymer and/or
Unsaturated olefin and/or multiple functional radical unsaturated compound for crosslinking, other (methyl) acrylate such as third that can be illustrated
E pioic acid methyl ester, (methyl) ethyl acrylate, (methyl) propyl acrylate, (methyl) butyl acrylate, the tertiary fourth of (methyl) acrylic acid
Ester, (methyl) hydroxy-ethyl acrylate, (methyl) acrylic acid aromatic ester etc.；Unsaturated olefin such as styrene, acrylonitrile, maleic acid spread out
Biology etc.；Such as two (methyl) acrylic acid glycol ester of multiple functional radical unsaturated compound, two (methyl) propylene acid propylene glycol esters, two
(methyl) acrylic acid butanediol ester, two (methyl) acrylic acid hexylene glycol esters, allyl methacrylate, triallyl cyanurate,
Divinylbenzene etc..The polymerization causes usually using known radical initiator, and the initiator is people from this field
Azo initiator such as AIBN and peroxide initiator such as BPO known to member, the dosage of initiator are usually monomer mixing
The 0.1-5% of object weight.
The main function of styrene-based polymer object is to coordinate plexiglass and butadiene graft is poly-
The index of refraction matching of object is closed, while improving the compatibility between two substances, to obtain outstanding optical effect and mechanical property.Institute
The index of refraction for the styrene-based polymer stated is 1.53-1.57, is preferably selected from poly- (methyl methacrylate-styrene-propylene
Nitrile) copolymer, poly- (styrene-acrylonitrile) copolymer, poly- (styrene-acrylonitrile-methyl methacrylate) copolymer,
One of poly- (acrylonitrile-methyl methacrylate) copolymer and poly- (styrene-methyl methacrylate) copolymer or
It is several；In further preferably poly- (styrene-acrylonitrile) copolymer and poly- (styrene-methyl methacrylate) copolymer
One or two.
Preferably, containing based on polymethyl methacrylate and styryl in the plexiglass
The 0-40wt% of total polymer weight, the preferably toughener of 10-30wt%.The toughener has core-shell structure, partial size ruler
Very little is 100-400nm.Its core be acrylic rubber, butadiene rubber, butadiene-styrene rubber, isoprene rubber, ethylene propylene diene rubber or
One or more of fluorine-silicon modified acrylic ester rubber, preferably acrylic rubber.The acrylic rubber is mainly
By (methyl) alkyl acrylate of 60-90% weight content C1-C20,5-35% weight containing such as fragrant second of copolymerizable monomer
The unsaturated polyfunctional monomer that alkenyl compound and 0.1-5% weight contain is polymerized.(methyl) propylene as C1-C20
Acid alkyl ester can be exemplified as (methyl) methyl acrylate, (methyl) ethyl acrylate, (methyl) propyl acrylate, (methyl) propylene
Acid butyl ester, (methyl) tert-butyl acrylate, (methyl) hydroxy-ethyl acrylate, (methyl) acrylic acid aromatic ester etc.；Aromatic ethylene base
Compound such as styrene, α-styrene etc.；Such as two (methyl) acrylic acid glycol ester of unsaturated polyfunctional monomer, two (methyl) third
Olefin(e) acid propylene glycol ester, two (methyl) acrylic acid butanediol esters, two (methyl) acrylic acid hexylene glycol esters, (methyl) acrylic acid allyl
Ester, triallyl cyanurate, divinylbenzene etc..The shell of toughener is by poly- (methyl) third based on nuclear weight 20-150%
Olefin(e) acid ester or its copolymer composition, the usual shell be mainly alkyl methacrylate by 50-100% weight containing C1-C20,
The unsaturated polyfunctional monomer of 0-50% copolymerizable monomer and 0-5% is polymerized.Copolymerizable monomer can illustrate such as
Alkyl acrylate, vinyl monomer such as acrylonitrile, aromatic ethenyl monomer such as styrene of C1-C20 etc.；It is unsaturated multifunctional
Such as two (methyl) acrylic acid glycol ester of monomer, two (methyl) propylene acid propylene glycol esters, two (methyl) acrylic acid butanediol esters, two
(methyl) acrylic acid hexylene glycol ester, (methyl) allyl acrylate, triallyl cyanurate, divinylbenzene etc..
The index of refraction of the butadiene graft polymer is 1.50-1.55, with 85% or more light transmittance, light transmission
Rate is according to ASTMD1003, with a thickness of being measured under the conditions of 2mm.The butadiene graft polymer contains the (first of 10-30wt%
Base) acrylic ester unit, described (methyl) acrylic ester unit can be exemplified as (methyl) methyl acrylate, (methyl) acrylic acid
Ethyl ester, (methyl) propyl acrylate, (methyl) butyl acrylate, (methyl) tert-butyl acrylate, (methyl) hydroxy-ethyl acrylate,
(methyl) acrylic acid aromatic ester etc..Preferably, the butadiene graft polymer is selected from (methyl) acrylate-fourth two
One or more of alkene-styrene-acrylonitrile polymer and (methyl) acrylate-butadiene-styrene polymer,
Further preferably methyl methacrylate-butadiene-styrene-acrylonitrile polymer.
In order to obtain optical effect outstanding, the plexiglass and butadiene graft polymer phase
Index of refraction difference is 0-0.03, preferably 0-0.01 between mutually.When index of refraction difference is larger, the light transmittance of product is bad.It produces
The index of refraction of product can be used following formula (one) and be calculated:
N=w1·n1+w2·n2+w3·n3+···+wi·ni(formula one)
Wherein: n indicates index of refraction；
niIndicate the index of refraction of i component；
wiThe weight fraction of i component in expression.
According to the present invention, processing aid can also be added in resin preparation process, the processing aid includes but is not limited to
Antioxidant, lubricant (release agent) etc., the antioxidant include positive 18 carbon of β-[3,5- di-tert-butyl-hydroxy phenyl] propionic acid
Alcohol ester, four [β-(3,5- di-tert-butyl-hydroxy phenyl) propionic acid] pentaerythritol esters, three [2,4- di-tert-butyl-phenyl] phosphorous acid
One or more of ester, bis- [2.4- di-tert-butyl-phenyl] pentaerythritol diphosphites etc., the dosage of antioxidant are methyl
The 0-2% of methacrylate resin weight；The lubricant is selected from pentaerythritol stearate, silicone powder, ethylene stearic bicine diester
One or more of amine etc., the dosage of lubricant are the 0-2% of polymethyl methacrylate resin weight.
The present invention also provides a kind of plexiglass/butadiene graft polymer composition preparation sides
Method includes the following steps:
S-1: polymethyl methacrylate of weighing in proportion, styrene-based polymer and optional toughener simultaneously mix equal
It is even；
S-2: the material being uniformly mixed in S-1 is subjected to extruding pelletization using double screw extruder and obtains polymethylacrylic acid
Late resin；
S-3: the plexiglass prepared in butadiene graft polymer and S-2 and mixing are weighed in proportion
Uniformly；
S-4: the material being uniformly mixed in S-3 is subjected to extruding pelletization using double screw extruder and obtains composition product；
Melt temperature in the step S-2 is 180-260 DEG C, screw speed 100-800rpm；
Melt temperature in the step S-4 is 180-260 DEG C, screw speed 100-800rpm.
Polymethyl methacrylate and styrene-based polymer are granulated, then again with butadiene graft polymer into
The product that row melt blending extruding pelletization obtains is preferably, this is because styrene-based polymer connects with butadiene in performance
The compatibility of branch polymer is better than the compatibility of styrene-based polymer and poly- methyl e pioic acid methyl ester, is granulated according to a step mixing
If, styrene-based polymer tends to be gathered in butadiene graft polymer, to cause polymethyl methacrylate
Disperse uneven influence properties of product, especially optical property with butadiene graft polymer.
Invention further provides a kind of plexiglass/butadiene graft polymer compositions to be used for
The purposes of home electric appliance housing, appliance panel, container etc..
Plexiglass provided by the invention/butadiene graft polymer composition has had both transparent, resistance to
Scraping, shock resistance and excellent machinability: 1) can using the butadiene graft polymer containing polymethyl methacrylate
To improve compatibility and dispersibility in butadiene graft polymer and plexiglass, to obtain good
Mechanical property and optical property；2) by the way that polymethyl methacrylate is added, the Scratch Resistance energy of alloy product is improved；3) lead to
Addition styrene-based polymer adjusting plexiglass is crossed to match with the index of refraction of butadiene graft polymer, from
And realize good optical property.
Specific embodiment
The following examples are used to illustrate the present invention, but are not intended to limit the scope of the present invention..In this application, " part " and
" % " by weight, unless otherwise prescribed.
1) correlative:
Methyl methacrylate-butadiene-styrene-acrylonitrile TR558A, index of refraction 1.52, LG chemistry；
Butadiene-styrene-acrylonitrile 8391, index of refraction 1.53, Shanghai Gaoqiao petrochemical industry；
Polymethyl methacrylate CM207, index of refraction 1.49, pencil hardness 4H, Qimei Industry Co., Ltd.；
Polystyrene-methyl methacrylate TX100S (content of polymethyl methacrylate is 60wt%), index of refraction
1.54, electrochemical Shanghai trade Co., Ltd；
Polystyrene-acrylonitrile 80HF, index of refraction 1.56, Ningbo LG Yong Xing Chemical Co., Ltd.；
Toughener 1: polybutadiene-styrene-acrylonitrile rubber powder HR181, South Korea's brocade lake petrochemical industry；
Toughener 2: polybutadiene-styrene-methyl methacrylate rubber powder EM500, LG chemistry；
Toughener 3: polyacrylate-methyl methacrylate rubber powder M210, Japanese Zhong Yuan；
Antioxidant: B900, Rianlon Corporation；
Lubricant: PETs sends out base chemicals (Zhangjiagang) Co., Ltd.
2) detection method:
Melt index: ASTM D1238；
Cantilever beam impact strength (non-notch): ASTM D256；
Heat distortion temperature；ASTM D648；
Vicat softening point: ASTM D1525；
Tensile strength: ASTM D638；
Pencil hardness (750g): ASTMD3363；
Light transmittance (2mm): ASTMD1003.
3) embodiment and comparative example:
The preparation of poly- methylpropionic acid methyl esters resin:
It is formulated according to table 1, then first accurate weighing each raw material component carries out each component of weighing in high speed mixer
Mixing, revolving speed 300rpm, incorporation time 8min, then use double screw extruder (L/D=40) in the case where revolving speed is 400rpm, it melts
Granulation extrusion is carried out under the conditions of 220 DEG C of temperature.
It takes resulting particle after above-mentioned extrusion to dry 4h under the conditions of 80 DEG C, is processed into corresponding batten, test its correlation
Performance, as a result such as table 1.
Embodiment 1-4:
It is formulated according to table 2, then first accurate weighing each raw material component carries out each component of weighing in high speed mixer
Mixing, revolving speed 300rpm, incorporation time 8min, then use double screw extruder (L/D=40) in the case where revolving speed is 400rpm, it melts
Granulation extrusion is carried out under the conditions of 220 DEG C of temperature.
It takes resulting particle after above-mentioned extrusion to dry 4h under the conditions of 80 DEG C, is processed into corresponding batten, test its correlation
Performance, as a result such as table 2.
Comparative example 1-7:
It is formulated according to table 2, then first accurate weighing each raw material component carries out each component of weighing in high speed mixer
Mixing, revolving speed 300rpm, incorporation time 8min, then use double screw extruder (L/D=40) in the case where revolving speed is 400rpm, it melts
Granulation extrusion is carried out under the conditions of 220 DEG C of temperature.
It takes resulting particle after above-mentioned extrusion to dry 4h under the conditions of 80 DEG C, is processed into corresponding batten, test its correlation
Performance, as a result such as table 2.
Comparative example 8:
The TR558A particle that market is obtained dry 4h under the conditions of 80 DEG C, is processed into corresponding batten, tests its correlation
Performance, as a result such as table 2.
Embodiment 5-9:
It is formulated according to table 3, then first accurate weighing each raw material component carries out each component of weighing in high speed mixer
Mixing, revolving speed 300rpm, incorporation time 8min, then use double screw extruder (L/D=40) in the case where revolving speed is 400rpm, it melts
Granulation extrusion is carried out under the conditions of 220 DEG C of temperature.
It takes resulting particle after above-mentioned extrusion to dry 4h under the conditions of 80 DEG C, is processed into corresponding batten, test its correlation
Performance, as a result such as table 3.
1. properties of product of table
| Name of material | PMMA-1 | PMMA-2 | PMMA-3 | PMMA-4 | PMMA-5 | PMMA-6 | PMMA-7 | PMMA-8 |
| CM207 | 50 | 60 | 70 | 50 | 60 | 80 | 50 | 80 |
| TX100S | \ | 40 | \ | 25 | \ | \ | \ | \ |
| 80HF | 50 | \ | 15 | 5 | 10 | 5 | 30 | \ |
| EM500 | \ | \ | 15 | \ | \ | \ | 10 | \ |
| M210 | \ | \ | \ | 20 | 30 | 15 | 10 | \ |
| HR181 | \ | \ | \ | \ | \ | \ | \ | 20 |
| Light transmittance (%) | 90 | 89 | 89 | 89 | 89 | 91 | 89 | 54 |
| Refraction index n | 1.52 | 1.51 | 1.51 | 1.51 | 1.50 | 1.49 | 1.51 | 1.48 |
2. properties of product of table
As seen from the results in Table 2, resulting composition have 80% or more light transmittance, pencil hardness reached H and
More than, embodiment 1-4 shows poly- using the butadiene graft containing polymethyl methacrylate unit compared with comparative example 6,7
It closes object and carries out the product translucency with higher that preparation is blended with plexiglass.Meanwhile embodiment 1-4 with
Comparative example 1-4 compares, by styrene-based polymer and polymethyl methacrylate first carry out after mixing granulation again with butadiene
It is preferably in optical property that graft polymers, which carries out mixing granulation resulting product,.In addition, the TR558A product with market
It compares, the Scratch Resistance of composition provided by the invention can significantly improve, and reach H rank.
3. properties of product of table
Claims (11)
1. a kind of plexiglass/butadiene graft polymer composition includes by weight following components:
(a) 100 parts of poly- methyl esters methacrylate resin
(b) butadiene graft polymer 40-200 parts,
It is preferred that 50-180 parts, it is 60-150 parts more preferable
The plexiglass and the mutual index of refraction difference of butadiene graft polymer is 0-0.03, excellent
It is selected as 0-0.01.
2. plexiglass according to claim 1/butadiene graft polymer composition, feature exist
In the index of refraction of the plexiglass is 1.49-1.55.
3. plexiglass according to claim 1 or 2/butadiene graft polymer composition, special
Sign is that the plexiglass is 50-95 parts by weight, the preferably polymethylacrylic acid of 60-90 parts by weight
Methyl esters and 5-50 parts by weight, the preferably blend of 10-40 parts by weight of styrene based polyalcohol, by 100 parts by weight polymethyls
Sour late resin meter.
4. plexiglass according to any one of claim 1-3/butadiene graft combination of polymers
Object, which is characterized in that polymethyl methacrylate is polymerized by the inclusion of the mixture of methyl methacrylate, the mixing
60 weight % are included at least in object, the preferably at least methyl methacrylate of 80 weight % and 0-40wt% can be with methacrylic acid
Other (methyl) acrylate and/or unsaturated olefin of methyl esters copolymerization and/or the multiple functional radical unsaturation chemical combination for crosslinking
Object, it is preferable that other (methyl) acrylate be selected from methyl acrylate, (methyl) ethyl acrylate, (methyl) propyl acrylate,
(methyl) butyl acrylate, (methyl) tert-butyl acrylate, (methyl) hydroxy-ethyl acrylate, in (methyl) acrylic acid aromatic ester
It is one or more；Unsaturated olefin is selected from one of styrene, acrylonitrile, maleic acid derivatives or a variety of；Multiple functional radical is not
Saturated compounds is selected from two (methyl) acrylic acid glycol esters, two (methyl) propylene acid propylene glycol esters, two (methyl) acrylic acid fourths
Diol ester, two (methyl) acrylic acid hexylene glycol esters, allyl methacrylate, triallyl cyanurate, in divinylbenzene
It is one or more.
5. plexiglass according to claim 1/butadiene graft polymer composition, feature exist
In the butadiene graft polymer has 85% or more light transmittance, index of refraction 1.50-1.55.
6. poly- plexiglass/butadiene graft polymer composition according to claim 3, feature
It is, the pencil hardness of the polymethyl methacrylate is 3-5H.
7. plexiglass according to claim 3/butadiene graft polymer composition, feature exist
In the index of refraction of the styrene-based polymer is 1.53-1.57, is selected from poly- ((methyl) acrylate-styrene-third
Alkene nitrile) copolymer, poly- (styrene-acrylonitrile) copolymer, one of poly- (styrene-(methyl) acrylate) copolymer
Or it is a variety of；Further preferably poly- (styrene-acrylonitrile) copolymer and poly- (styrene-methyl methacrylate) copolymer
One of or it is a variety of.
8. plexiglass according to claim 5/butadiene graft polymer composition, feature exist
In (methyl) acrylic ester unit in the butadiene graft polymer containing 10-30wt%, preferred butadiene connects
Branch polymer is (methyl) acrylate-butadiene-styrene-acrylonitrile polymer and (methyl) acrylate-fourth two
One of alkene-styrene polymer is a variety of, further preferably methyl methacrylate-butadiene-styrene-third
Alkene nitrile polymer.
9. plexiglass according to claim 1 or 2/butadiene graft polymer composition, special
Sign is, containing based on polymethyl methacrylate and styrene-based polymer in the plexiglass
The 0-40wt% of total weight, the preferably toughener of 10-30wt%；
The toughener has core-shell structure, partial size 100-400nm, and shell is poly- (methyl) acrylate or its copolymerization
Object, core are acrylic rubber, butadiene rubber, butadiene-styrene rubber, isoprene rubber, ethylene propylene diene rubber or fluorine-silicon modified acrylic ester
One of rubber is a variety of, preferably acrylic rubber.
10. a kind of described in any item plexiglasses/butadiene graft polymer group of such as claim 1-9
Close the preparation method of object, comprising the following steps:
S-1: weigh polymethyl methacrylate, styrene-based polymer and optional toughener and is uniformly mixed in proportion；
S-2: the material being uniformly mixed in S-1 is subjected to extruding pelletization using double screw extruder and obtains polymethyl methacrylate
Resin；
S-3: the plexiglass prepared in butadiene graft polymer and S-2 is weighed in proportion and is mixed equal
It is even；
S-4: the material being uniformly mixed in S-3 is subjected to extruding pelletization using double screw extruder and obtains poly-methyl methacrylate
Ester/butadiene graft polymer composition product；
Preferably, the melting temperature in the step S-2 is 180-260 DEG C, screw speed 100-800rpm；
Preferably, the melting temperature in the step S-4 is 180-260 DEG C, screw speed 100-800rpm.
11. a kind of described in any item plexiglasses/butadiene graft polymer group of such as claim 1-9
It closes plexiglass/butadiene graft polymer composition prepared by object or claim 10 and is used for household electrical appliances shell
The purposes of body, appliance panel, container.
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| CN114369329A (en) * | 2021-12-29 | 2022-04-19 | 上海金发科技发展有限公司 | Transparent solvent-resistant composition and preparation method thereof |
| CN114369329B (en) * | 2021-12-29 | 2024-04-30 | 上海金发科技发展有限公司 | Transparent solvent-resistant composition and preparation method thereof |
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