CN1148609A - Styrene series resin composition - Google Patents
Styrene series resin composition Download PDFInfo
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- CN1148609A CN1148609A CN 96109456 CN96109456A CN1148609A CN 1148609 A CN1148609 A CN 1148609A CN 96109456 CN96109456 CN 96109456 CN 96109456 A CN96109456 A CN 96109456A CN 1148609 A CN1148609 A CN 1148609A
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Abstract
The present invention discloses a low-odour styrene system resin composite which:(1) 100 portions (weight) of styrene system resin, consisting of 5-100 wt% rubber-like graft copolymer (A) and 0-95 wt% styrene system copolymer (B), in which the rubber-like graft copolymer A is obtained by using 50-90 wt% styrene system monomer, 10-50 wt% acrylonitrile system monomer and 0-40 wt% copolymerizable monomer, and making them pass through the process of graft copolymerization in the presence of rubber-like palymer; (2) 0.005-15 portions (weight) of sesquiterpene compound (C). The invented styrene system resin composite possesses low odour and optimum material balance, and can be made into various formed products.
Description
The invention relates to a kind of styrene resin composite, or rather, the invention relates to that a kind of low odor, rerum natura balance are good, be fit to the styrene resin composite of prolonged operation person and various processing, the method for forming.
Styrene resin composite is to be scattered in a kind of impact resistance resin composition made in the styrene based copolymer with rubber like graft copolymer.With regard to application, phenylethylene resin series must be through various processing, the method for forming (as, time processing: ejection formation, extrusion moulding etc.; Secondary processing: vacuum forming etc.) can make the moulding commodity.Paid attention to day by day at environmental protection ideas, under the trend of hommization, the smell quality of working space day by day is subjected to operator's attention then to Working environment day by day.As everyone knows, various moulding, processing method all can be supervened the peculiar smell of resin uniqueness, can't be fully and operator isolate.Therefore, develop a kind of low odor and do not damage its rerum natura balance, be fit to prolonged operation person's styrene resin composite, become the problem that the present technique field demands urgently breaking through then.
For reducing phenylethylene resin series at the stink of processing, formative stage produced, existing mode of ameliorating is to add antioxidant in manufacturing processed, strengthen waving and take off, in the hope of reducing levels of residual monomers, reach the purpose that reduces stink, its method is disclosed in for example patent case such as Japanese kokai publication hei 7-149817 and Japanese kokai publication hei 7-149818; But aforesaid method is limited to the improvement of stink, and because of only reducing a kind of of the numerous sources of stink, and the reduction amount is limited; With regard to general processing environment now, still be not suitable for prolonged operation person's operations such as (as:) penetrating, extrude, because aforesaid method only can reach and postpone the operator and feel time of stink.
In view of this, this case contriver is at the deficiencies in the prior art, develop a kind of the popularization and be applicable to all processing and manufacturing processes, and suitable prolonged operation person's the low odor and the styrene resin composite of detriment sexual balance not.
The object of the present invention is to provide a kind of low odor and rerum natura balance good, the polystyrene oil/fat composition that is fit to prolonged operation person, the preparation method of this styrene resin composite is included in to make and adds a sesquiterpene of taking from natural phant in the process of mixing, so can effectively remove at this mix process and processing thereafter, the stink that produces in the moulding process, produce an approximate light smell of fine quality of timber, think that the prolonged operation personnel accept.
Low odor of the present invention and rerum natura balance are good, and the styrene resin composite that is fit to long-term prolonged operation person comprises:
The phenylethylene resin series of (1) 100 part of weight, form by 5～100 weight % rubber like graft copolymer (A) and 0～95 weight % styrene based copolymer (B), wherein, rubber like graft copolymer (A) gets with 50～90 weight % styrenic monomers, 10～50 weight % acrylic monomers and 0～40 weight % copolymerizable monomer graft copolymerization for the rubber-like polymer exists down; And
The sesquiterpenoid (C) of (2) 0.005～15 parts of weight.
Above-mentioned composition can make one after mixing to can be applicable to low odor, the rerum natura balance of any moulding, processing method good, and suitable prolonged operation person's styrene resin composite.
Rubber like graft copolymer of the present invention (A) be by the rubber-like polymer with based on the amount of monomer of 100 weight %, 50～90 weight % styrenic monomers, 10～50 weight % acrylic monomers and 0～40 weight % copolymerizable monomer, can make via bulk, solution, suspension or emulsion polymerization effect, also can make via the combination of these polymerizations, as: emulsification-bulk or bulk-suspension polymerization effect; Preferred methods is emulsion polymerization method, block polymerization and solution polymerization process; Best is emulsion polymerization method.
Emulsion polymerization and rubber like graft copolymer (A) more preferably condition be to exist down in the diene series rubber emulsion, getting weight average particle diameter with 50～90 weight % styrenic monomers, 10～50 weight % acrylic monomers and 0～40 weight % copolymerizable monomer graft polymerization is the emulsion of 0.05～0.8 micron rubber graft copolymer (A), wherein, the rubber-like polymer accounts for 15～85 weight % usually, and that preferable is 45～80 weight %; Thereafter through condense, dehydration, drying and other steps, make powder granulous rubber graft copolymer (A).Above-mentioned diene series rubber emulsion comprises the conjugate diene monomer of 60～100 weight % and the formed same membered copolymer of unit unsaturated monomer of 0～40 weight %, or its multipolymer.Above-mentioned conjugate diene monomer can be represented by following formula:
Wherein, R can be hydrogen, methyl or chloro etc.Copolymerizable unsaturated monomer can be styrenic monomers, acrylic monomer, (methyl) acrylic ester monomer.
Above-mentioned diene series rubber emulsion can be polyhutadiene, butadiene-styrene copolymer, perbutan, divinyl-methylmethacrylate copolymer or isoprene-butyl acrylate copolymer etc.Can become weight average particle diameter with above-mentioned monomer direct polymerization is 0.05～0.8 micron polymkeric substance, or can aggregate into the loose rubber latex that becomes 0.2～0.8 micron of 0.05～0.18 micron small particle size rubber latex in advance.The loose method of above-mentioned rubber comprises the chemical loose method of the polymer coagulant that adds organic acid, metal-salt or carboxylic acid group etc.The loose method of this chemistry for example can use butyl acrylate-Sipacril 2739OF as polymer coagulant.
Through above-mentioned emulsion process polymerization and rubber graft copolymer (A) (be called for short emulsification graft copolymer) have unimodal formula size distribution, median size is 0.05～0.8 micron, or have the double-peak type size distribution, median size is respectively 0.05～0.18 micron and 0.2～0.8 micron.
Bulk or solution polymerization process polymerization and the manufacture method of rubber like graft copolymer (A) be that diene series rubber is dissolved in monomer mixture and/or the solvent in advance, this monomer mixture comprises the copolymerizable monomer of 50～90 weight % styrenic monomers, 10～50 weight % acrylic monomers and 0～40 weight %, then gained solution is pumped in the reactor, mix down and carry out graft polymerization reaction.Can add according to circumstances between the reaction period an amount of initiator, chain-transfer agent (for example: uncle-lauryl mercaptan (tert-dodecylmercaptan)), with controlled polymerization speed, percentage of grafting or polymericular weight.Reactor can be combined by a plurality of devices, and preferable is the still type reactor of having strong mixer.The optional usefulness of above-mentioned solvent is for example: toluene, dimethylbenzene, ethylbenzene, methylethylketone, vinyl acetic monomer etc.
Above-mentioned diene series rubber more preferably is divinyl rubber, synthetic polyisoprene, neoprene etc.Divinyl rubber has the branch of high-cis and low cis, in the high-cis rubber, the typical weight of its cis/vinyl consists of 94～98%/1～5%, all the other compositions then have transconfiguration, its mooney viscosity (Mooney Viscosity) is between 20～120, molecular weight ranges is with 100,000～800, and 000 is preferable; In the low cis rubber, it is 20～40%/1～20% that the typical weight of cis/vinyl is formed, all the other are transconfiguration, its mooney viscosity is between 20～120, and other elastomeric material that is fit to also comprises: acrylonitrile/butadiene rubber, styrene/butadiene rubbers (styrene butadiene rubber sbr that promptly is commonly called as).The polymerization pattern of the phenylethylene/butadiene copolymerization rubber that the present invention is suitable for can be two-section type (di-block) copolymerization, syllogic (tri-block) copolymerization, random (random) copolymerization or star formula (startype) copolymerization, what the part by weight scope of styrene/butadiene rubbers was preferable is 5/95 to 80/20, what molecular weight ranges was preferable is 50,000～600,000.Above-mentionedly be applicable to that rubber of the present invention is more preferably for elastoprene and styrene/butadiene rubbers.
By bulk or solution polymerization process polymerization and rubber graft copolymer (A) (being called for short bulk or solution graft copolymerization thing), its average rubber particle size is generally between 0.6～10 micron, preferable is 1.0～7.0 microns, wherein, the rubber-like polymer accounts for 3～25 weight % usually, and that preferable is 4～15 weight %.
Rubber like graft copolymer of the present invention (A) also can form the size distribution of bimodal or three peak formulas with said two devices and usefulness except using above-mentioned emulsification graft copolymer or bulk (or solution) graft copolymerization beyond the region of objective existence individually:
The double-peak type person as:
(1) 0.2～0.8 micron of median size (emulsification)
0.6～10 micron of median size (bulk or solution)
Or
(2) 0.05～0.18 micron of median size (emulsification)
0.6～10 micron (bulk or solution) three peak formula person of median size as:
0.05～0.18 micron of median size (emulsification)
0.2～0.8 micron of median size (emulsification)
0.6～10 micron of median size (bulk or solution)
Above-mentioned median size is that sample is through OsO
4After (perosmic anhydride) dyeing,, obtain with following formula again with the particle diameter of 1000 particles of transmission electron microscope mensuration:
Median size=∑ nD
4/ ∑ nD
3(D is a particle diameter, and n is a population)
Styrenic monomers used in the present invention can be selected from vinylbenzene, alpha-methyl styrene ,-chloro-styrene, right-tert-butyl vinylbenzene, p-methylstyrene, neighbour-chloro-styrene, right-chloro-styrene, 2,5-dichlorostyrene, 3,4-dichlorostyrene, 2,4,6-tribromo-benzene ethene, 2, the 5-Dowspray 9; With vinylbenzene or alpha-methyl styrene is preferable.
Acrylic monomer used in the present invention can comprise vinyl cyanide or Alpha-Methyl vinyl cyanide; With vinyl cyanide is preferable.
The copolymerizable monomer of using in the rubber like graft copolymer of the present invention (A) can be selected from (methyl) acrylic ester monomer, maleimide is monomer, vinylformic acid, methacrylic acid, Maleic Acid, Anhydrous and glycolmethacrylate.(methyl) acrylic ester monomer can be methyl methacrylate, Jia Jibingxisuanyizhi, propyl methacrylate, butyl methacrylate, methacrylic acid dodecane ester, methacrylic acid 2-carboxylic ethyl ester, glycidyl methacrylate or Dimethylaminoethyl Methacrylate, methyl acrylate, butyl acrylate; More preferably be methyl methacrylate, butyl acrylate.
Maleimide is that monomer is to be selected from maleimide, N-methyl maleimide, N-octyl group maleimide, N-dodecyl maleimide, N-cyclohexyl maleimide, N-phenylmaleimide, N-2,3-tolyl maleimide, N-2,4-tolyl maleimide, N-2,3 ethylbenzene base maleimides, N-2,4-ethylbenzene base maleimide, N-2,3-butylbenzene base maleimide, N-2,4-butylbenzene base maleimide, N-2,6-tolyl maleimide, N-2,3-chloro-phenyl-maleimide, N-2,4-chloro-phenyl-maleimide, N-2,3-bromophenyl Malaysia imide, N-2,4-bromophenyl Malaysia imide; With the N-phenylmaleimide is best.
Styrene based copolymer used in the present invention (B) is to be got by the copolymerizable monomer polymerization of the acrylic monomer of the styrenic monomers of 50～90 parts of weight, 10～50 parts of weight and 0～40 part of weight optionally.This styrenic monomers, acrylic monomer and copolymerizable monomer are identical with employed monomer explanation in the rubber like graft copolymer (A).This styrene based copolymer (B) can also bulk, solution, suspension or emulsion polymerization method make, with bulk and solution polymerization process is preferable, its weight average molecular weight scope is 60, between 000 to 400,000, and the number molecular-weight average is 30,000 to 200, between 000, will cause processing to be difficult for if molecular weight is too high, if the too low then shock-resistance of molecular weight is not good; Rubber-like polymer of the present invention accounts for 3～30 weight % of rubber like graft copolymer (A) and styrene based copolymer (B) total amount usually, is preferably 5～25 weight %.
Being fit to sesquiterpenoid used in the present invention (C) is molecular formula C
15H
24The common name of compound, comprise cadinene (cadinenes) is for example arranged, caryophyllene (caryophyllene), alkene (copaene), α-farnesene (α-famesene), β-farnesene (β-famesene), Humuleno (humulene), longifolene (longifolene), thujopsene (thujopsene) or perfume tree ellagic acid (ylangene), its consumption is between 0.005～15 part of weight, more preferably for being 0.01～5 part of weight, the too low deodorizing effect of consumption is not obvious, and too high then rerum natura balance descends to some extent.
The sesquiterpene (C) of above-mentioned 5～100 weight % rubber like graft copolymer (A), 0～95 weight % styrene based copolymer (B) and 0.005～15 part of weight is complied with the process fusion of generally mixing, but can make the styrene resin composite that the present invention has low odor, good, the suitable prolonged operation person of rerum natura balance and widespread use.
The employed device that mixes comprises single or twin screw extruder, mix cylinder and inside mix device etc.Can select according to circumstances in the styrene resin composite of the present invention to use as additives such as photostabilizer, the mobile auxiliary agent of lubricant, UV light absorber, antioxidant, thermo-stabilizer, static inhibitor, weighting agent, glass fibre, processing aid, pigment.
For further specifying the present invention, be described as follows the composition unless specifically stated otherwise of composition, otherwise all represent now with example:＜preparation example one with part weight〉preparation of rubber like graft copolymer (A-1):
Composition part weight
1,3-butadiene 150.00
Potassium persulfate solution (1%) 15.00
Potassium oleate 2.00
Distilled water 190.00
Ethylene glycol dimethacrylate 0.13
Above-mentioned prescription reacted 12 hours under 65 ℃ of temperature, can get transformation efficiency and be 94%, solids content is about 40%, and weight average particle diameter is 0.1 micron a synthetic rubber latex.
Use following composition manufacturing to contain carboxylic acid group's polymer coagulant in addition:
Composition part weight
Ethyl propenoate 90.00
Methacrylic acid 10.00
Potassium persulfate solution (1%) 0.50
Sodium dodecyl sulfate solution (10%) 1.00
Just-lauryl mercaptan 1.00
Distilled water 200.00
Above-mentioned prescription reacted 5 hours under 75 ℃ of temperature, can get that transformation efficiency is about 95%, pH value be 6.0 contain carboxylic acid group's polymer coagulant.
Afterwards, utilize 3 parts of weight to contain the synthetic rubber latex (dry weight) that the high molecular agglutinant of carboxylic acid group (dry weight) comes loose 100 parts of weight, the pH value of gained enlarged rubber emulsion is 8.5, and weight average particle diameter is about 0.31 micron.
At last, the enlarged rubber emulsion is carried out graft polymerization reaction according to following prescription, to make rubber like graft copolymer (A-1).
Composition part weight
Enlarged rubber emulsion (dry weight) 100.0
Vinylbenzene 25.0
Vinyl cyanide 8.3
Potassium oleate 1.2
Uncle-lauryl mercaptan 2.0
Cumene hydroperoxide hydrogen 3.0
Copperas solution (0.2%) 3.0
Formaldehyde sodium sulfoxylate solution (10%) 0.90
7 diamines, four acetums (0.25%) 3.0
Distilled water 200.0
After obtained rubber-like graft emulsion condenses with calcium chloride, can make the rubber like graft copolymer (A-1) (rubber content is 75 weight %) that the present invention wishes to get, its weight average particle diameter is 0.3 1 microns.
＜preparation example two〉preparation of rubber like graft copolymer (A-2):
Composition part weight
Synthetic rubber latex (0.1 micron) (dry weight) 100.0
Vinylbenzene 32.4
Vinyl cyanide 12.6
Potassium oleate 1.5
Uncle-dodecyl base mercaptan 2.0
Cumene hydroperoxide hydrogen 3.0
Copperas solution (0.2%) 3.0
Formaldehyde sodium sulfoxylate solution (10%) 0.9
Ethylene dinitrilotetra-acetic acid solution (0.25%) 3.0
Distilled water 200.0
Can make the rubber like graft copolymer (A-2) (rubber content is 69 weight %) that the present invention is wished to get after the rubber-like graft emulsion that above-mentioned prescription makes condenses with calcium chloride, its weight average particle diameter is 0.1 micron.
＜preparation example three〉preparation of rubber like graft copolymer (A-3):
Use the polyhutadiene (company of Asahi Chemical Industry produces, and commodity are called Asadene55AS) of 6.6 parts of weight numbers, the benzoyl peroxide of the uncle-lauryl mercaptan of 0.1 part of weight and 0.07 part of weight is as initiator.Above-mentioned composition is dissolved in fully in the ethylbenzene of the vinyl cyanide of the vinylbenzene of 74.4 parts of weight, 25.6 parts of weight and 30 parts of weight, form feedstock solution, it is in 44 liters first reactor that this feedstock solution is sent into volume continuously, temperature of reaction is 100 ℃, dispose screw mixer in the reactor, its stir speed (S.S.) is 300rpm; In the agitator and be provided with the refrigeration cycle pipe.To take out continuously and send in second reactor through the mixture behind first reactor reaction, the device of this second reactor be identical with this first reactor.The transformation efficiency of thing to be mixed reaches at 60% o'clock, mixture is taken out send in the devolatilization device, removes after unreacted monomer and the volatile matter, it is extruded granulation, can make rubber like graft copolymer (A-3), the weight average particle diameter of its rubber is about 1.1 microns, and rubber content is 11 weight %.
Following is the rerum natura of example of the present invention and the obtained product of comparative example and the testing standard of molded appearance:
* tensile strength: according to ASTM D-638, with kg/cm
2Expression.
* Emhorn shock strength (IZOD): according to AS the test of M D-256 regulation, represent with kgcm/cm.
* melt flow index (MI):, represent with g/10min according to the test of ASTM D1238 regulation.
With the phenylethylene resin series polymkeric substance that makes, extrude through a twin screw extruder, under the gas situation that does not detach its die head place generation, assess the taste of its generation.Went through continuously one hour by the above evaluation group that forms of three people (containing), assess that taste could be accepted and prolonged operation under amenity.Unanimous being assessed as is recorded as " zero " in the time of can accepting, as if having any people to do not feel like oneself or thinking not good then be assessed as " * " of taste.
Examples Example 1:
This example uses 100 parts of weight of styrene resin of being made up of 18.7 weight % (preparation example one) gained rubber like graft copolymer (A-1) and 81.3 weight % styrene based copolymers (B).The weight average molecular weight (M) of styrene based copolymer (B) is 130,000, and number molecular-weight average (M) is 67,000, and wherein acrylonitrile content accounts for 28 weight %, and styrene content accounts for 72 weight %, and the rubber content of styrene resin is 14 weight %;
Then add the sesquiterpene Sesquiterpene (YASUHARA Chem. ) of 1.0 parts of weight, form a homogeneous melt.This melt is squeezed into bar, and cuts into particulate state, carry out the evaluation of physical property measurement and smell; The results are shown in table one and table two.Example 2:
Repeat example 1, different is (A-1) ratio of (B) relatively, and the weight average molecular weight (Mw) of used styrene based copolymer (B) is 140,000, number molecular-weight average (Mn) is 69,000, acrylonitrile content is 24 weight %, styrene content is 76 weight %, and the rubber content of styrene resin is 23.5 weight %, and the evaluation of only carrying out smell; The results are shown in table.Example 3:
Repeat example 1, the sesquiterpene (Sesquiterpene) of 0.1 part of weight that different are to use the results are shown in table one and table two.Example 4:
Repeat example 1, the consumption of different is sesquiterpene (Sesquiterpene ) is 5.0 parts of weight; The results are shown in table one and table two.Example 5:
Repeat example 1, but rubber like graft copolymer (A) accounts for 23.3%, wherein 9.3 weight % are rubber like graft copolymer (A-1), and 14 weight % are rubber like graft copolymer (A-2).Example 6:
The styrene resin that this example uses the sesquiterpene (Sesquiterpene ) of the rubber like graft copolymer (A-3) of 100 weight % and 1.0 parts of weight to be formed carries out the physical property measurement and the smell assessment of product equally; The result is stated from table one.Example 7:
Repeat example 1, but rubber like graft copolymer (A) accounts for 44.5%, and wherein 16.5 weight % are rubber like graft copolymer (A-1), and 28 weight % are rubber like graft copolymer (A-3), and use the higher styrene based copolymer of molecular weight (B) (Mw=230,000 instead; Mn=120,000); The result is stated from table one.Example 8:
Repeat example 7, but rubber like graft copolymer (A) accounts for 42.2%, wherein 8.9 weight % are rubber like graft copolymer (A-1), and 13.3 weight % are rubber like graft copolymer (A-2), and 20 weight % are rubber like graft copolymer (A-3); The result is stated from table one.Comparative example 1:
After according to the contained prescription of table one raw material being mixed, carry out the smell assessment transitivity test of product with example 1; The result is stated from table one and table two; Be presented at and do not add under the sesquiterpene situation, frowziness produces.Comparative example 2:
Repeat comparative example 1, but add the sesquiterpene Sesquiterpene of 0.001 part of weight; The result is stated from table one and table two; Show when sesquiterpene Sesquiterpene addition very little the time still frowziness generation.Comparative example 3:
Repeat comparative example 1, but add the sesquiterpene Sesquiterpene of 20.0 parts of weight; The result is stated from table one and table two; Show that the special odor of its generation is too dense, is not suitable for prolonged operation, and causes melt flow index obviously to rise when the sesquiterpene consumption is too much.Comparative example 4:
Repeat comparative example 1, but add the terpinolene Terpinolene of 2.0 parts of weight; The result is stated from table one; Show that obtained composition also can't remove stink fully, its lower boiling and destabilization character also limit its range of application.Comparative example 5:
Repeat comparative example 4, but use the kautschin Dipentene of 2.0 parts of weight instead; The result is stated from table one; Show that obtained composition can't remove stink.Comparative example 6:
Repeat comparative example 4, but use the limonene Limonene of 2.0 parts of weight instead; The result is stated from table one; Show that obtained composition can't remove stink.Comparative example 7:
Repeat comparative example 4, but use the vanilla flavor Vanilla Spice of 2.0 parts of weight instead; The result is stated from table one; Show that obtained composition not only can't remove stink, and can produce a kind of strange taste.Comparative example 8:
Repeat comparative example 4, but use the lavender spices Lavender Spice of 2.0 parts of weight instead; The result is stated from table one; Show that obtained composition produces strong special smell, can cause the respiratory tract discomfort, be not suitable for prolonged operation person, and can't remove stink.Comparative example 9:
Repeat comparative example 1, but use the lower styrene based copolymer of molecular weight (B) instead, and add the sesquiterpene Sesquiterpene of 1.0 parts of weight; Obtained composition has deodorizing effect, but because of rerum naturas such as impact strength are low excessively, so lost its using value.
By above test as can be known, the test of comparative example 4～8 for using sesquiterpene Sesquiterpene various spices in addition to add, the neither ideal of result of its stink assessment.
| Table one | Example 1 | Example 2 | Example 3 | Example 4 | Example 5 | Example 6 | Example 7 | Example 8 | Comparative example 1 | Comparative example 2 | Comparative example 3 | Comparative example 4 | Comparative example 5 | Comparative example 6 | Comparative example 7 | Comparative example 8 | |||
| Phenylethylene resin series | Rubber like graft copolymer (A) | Rubber like graft copolymer (A-1) | Weight % | ??18.7 | 31.3 | ?18.7 | 18.7 | ???9.3 | ????- | ??16.5 | ??8.9 | ???18.7 | ????18.7 | ????18.7 | ??18.7 | ???18.7 | ???18.7 | ???18.7 | ???18.7 |
| Rubber like graft copolymer (A-2) | Weight % | ?????- | ???- | ????- | ???- | ??14.0 | ????- | ????- | ?13.3 | ??????- | ???????- | ???????- | ?????- | ??????- | ??????- | ??????- | ?????- | ||
| Rubber like graft copolymer (A-3) | Weight % | ?????- | ???- | ????- | ???- | ?????- | ??100 | ????28 | ???20 | ??????- | ???????- | ???????- | ?????- | ??????- | ??????- | ??????- | ?????- | ||
| Styrene based copolymer (B) | Content | Weight % | ??81.3 | 68.7 | ?81.3 | 81.3 | ??76.7 | ????- | ??55.5 | ?57.8 | ???81.3 | ????81.3 | ????81.3 | ??81.3 | ???81.3 | ???81.3 | ???81.3 | ??81.3 | |
| Weight average molecular weight (Mw) | ?×10000 | ????13 | ??14 | ???13 | ??13 | ????13 | ????- | ????23 | ???23 | ?????13 | ??????13 | ??????13 | ????13 | ?????13 | ?????13 | ?????13 | ????13 | ||
| Number molecular-weight average (Mn) | ?×10000 | ???6.7 | ?6.9 | ??6.7 | ?6.7 | ???6.7 | ????- | ????12 | ???12 | ????6.7 | ?????6.7 | ?????6.7 | ???6.7 | ????6.7 | ????6.7 | ????6.7 | ???6.7 | ||
| Vinyl cyanide | Weight % | ????28 | ??24 | ???28 | ??28 | ????28 | ????- | ????28 | ???28 | ?????28 | ??????28 | ??????28 | ????28 | ?????28 | ?????28 | ?????28 | ????28 | ||
| Vinylbenzene | Weight % | ????72 | ??76 | ???72 | ??72 | ????72 | ????- | ????72 | ???72 | ?????72 | ??????72 | ??????72 | ????72 | ?????72 | ?????72 | ?????72 | ????72 | ||
| Sesquiterpene (Sesquiterpene) | Part weight | ???1.0 | ?1.0 | ??0.1 | ?5.0 | ??1.0 | ??1.0 | ??1.0 | ??1.0 | ??????0 | ???0.001 | ????20.0 | ?????- | ??????- | ??????- | ??????- | ?????- | ||
| Terpinolene (Terpinolene) | Part weight | ?????- | ???- | ????- | ???- | ????- | ????- | ????- | ????- | ??????- | ???????- | ???????- | ???2.0 | ??????- | ??????- | ??????- | ?????- | ||
| Kautschin (Dipentene) | Part weight | ?????- | ???- | ????- | ???- | ????- | ????- | ????- | ????- | ??????- | ???????- | ???????- | ?????- | ????2.0 | ??????- | ??????- | ?????- | ||
| 1,8-terpadiene (Limonene) | Part weight | ?????- | ???- | ????- | ???- | ????- | ????- | ????- | ????- | ??????- | ???????- | ???????- | ?????- | ??????- | ????2.0 | ??????- | ?????- | ||
| Vanilla flavor (Vanilla Spice) | Part weight | ?????- | ???- | ????- | ???- | ????- | ????- | ????- | ????- | ??????- | ???????- | ???????- | ?????- | ??????- | ??????- | ????2.0 | ?????- | ||
| Clothing hay-scented material (Lavender Spice) | Part weight | ????- | ???- | ????- | ???- | ????- | ????- | ????- | ????- | ??????- | ???????- | ???????- | ?????- | ??????- | ??????- | ??????- | ???2.0 | ||
| The rubber content of phenylethylene resin series | Weight % | ???14 | 23.5 | ???14 | ??14 | ?16.6 | ???11 | ??15.5 | ???18 | ?????14 | ??????14 | ??????14 | ????14 | ?????14 | ?????14 | ?????14 | ????14 | ||
| The smell evaluation | ???○ | ??○ | ???○ | ??○ | ???○ | ???○ | ???○ | ???○ | ?????× | ???????× | ??????× | ?????× | ?????× | ?????× | ?????× | ?????× | |||
| Remarks | Stink is dense | Frowziness | It is too dense to distinguish the flavor of | Frowziness | Frowziness | Frowziness | Strange taste | Cause the respiratory tract discomfort | |||||||||||
| Table two | Example 1 | Example 3 | Example 4 | Comparative example 1 | Comparative example 2 | Comparative example 3 | Comparative example 9 | |||
| Rubber like graft copolymer (A) | Rubber like graft copolymer (A-1) | Weight % | ??18.7 | ??18.7 | ??18.7 | ???18.7 | ??18.7 | ???18.7 | ???18.7 | |
| Rubber like graft copolymer (A-2) | Weight % | ???- | ???- | ???- | ???- | ???- | ????- | ???- | ||
| Rubber like graft copolymer (A-3) | Weight % | ???- | ???- | ???- | ???- | ???- | ????- | ???- | ||
| Styrene based copolymer (B) | Content | Weight % | ???81.3 | ???81.3 | ???81.3 | ???81.3 | ???81.3 | ???81.3 | ???81.3 | |
| Weight average molecular weight (Mw) | ×10000 | ???13 | ???13 | ???13 | ???13 | ???13 | ???13 | ???13 | ||
| Number molecular-weight average (Mn) | ×10000 | ???6.7 | ???6.7 | ???6.7 | ???6.7 | ???6.7 | ???6.7 | ???6.7 | ||
| Vinyl cyanide | Weight % | ???28 | ???28 | ???28 | ???28 | ???28 | ???28 | ???28 | ||
| Vinylbenzene | Weight % | ???72 | ???72 | ???72 | ???72 | ???72 | ???72 | ???72 | ||
| Sesquiterpene (sesquiterpene) | Part weight | ???1.0 | ???0.1 | ???5.0 | ???0 | ???0.001 | ???20.0 | ???1.0 | ||
| The rubber content of phenylethylene resin series | Weight % | ???14 | ???14 | ???14 | ???14 | ???14 | ???14 | ???14 | ||
| Tensile strength | ??????????kg/cm 2 | ???485 | ???483 | ???485 | ???487 | ???485 | ???473 | ???430 | ||
| Emhorn shock strength (IZOD) | ??????????kg·cm/cm | ???19.1 | ???19.0 | ???18.7 | ???19.2 | ???19.0 | ???18.2 | ???6.1 | ||
| Melting flow index (MI) | ??????????g/10min | ???1.7 | ???1.7 | ???1.7 | ???1.7 | ???1.7 | ???2.3 | ???9.5 | ||
Claims (7)
1, a kind of styrene resin composite, it is characterized in that said composition be by
The phenylethylene resin series of (1) 100 part of weight, form by 5～100 weight % rubber like graft copolymer (A) and 0～95 weight % styrene based copolymer (B), wherein, rubber like graft copolymer (A) gets with 50～90 weight % styrenic monomers, 10～50 weight % acrylic monomers and 0～40 weight % copolymerizable monomer graft copolymerization for the rubber-like polymer exists down; And
Sesquiterpenoid (C) combination of (2) 0.005～15 parts of weight.
2, composition according to claim 1 is characterized in that, rubber like graft copolymer (A) makes with emulsion polymerization method, and its median size is 0.05～0.8 micron.
3, composition according to claim 1 is characterized in that, rubber like graft copolymer (A) is the emulsification graft copolymer, and its particle diameter has double-peak type and distributes, and is respectively 0.05～0.18 micron, 0.2～0.8 micron.
4, composition according to claim 1 is characterized in that, rubber like graft copolymer (A) makes with bulk or solution polymerization process, and its median size is 0.6～10 micron.
5, composition according to claim 1, it is characterized in that, rubber like graft copolymer (A) is formed by emulsification graft copolymer and bulk or solution graft copolymerization thing, its weight average particle diameter is respectively: 0.05～0.18 micron, 0.2～0.8 micron of emulsification graft copolymer, 0.6～10 micron of bulk or solution graft copolymerization thing.
6, composition according to claim 1 is characterized in that, the weight average molecular weight of styrene based copolymer (B) is 60,000 to 400,000, and the number molecular-weight average is 20,000 to 30,000.
7, composition according to claim 1 is characterized in that, the content of sesquiterpene (C) is 0.01～5 part of weight.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN96109456A CN1051565C (en) | 1996-08-23 | 1996-08-23 | Styrene series resin composition |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN96109456A CN1051565C (en) | 1996-08-23 | 1996-08-23 | Styrene series resin composition |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1148609A true CN1148609A (en) | 1997-04-30 |
| CN1051565C CN1051565C (en) | 2000-04-19 |
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Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN96109456A Expired - Fee Related CN1051565C (en) | 1996-08-23 | 1996-08-23 | Styrene series resin composition |
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| Country | Link |
|---|---|
| CN (1) | CN1051565C (en) |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102164974B (en) * | 2008-09-04 | 2012-11-21 | 阿迈瑞斯公司 | Farnesene interpolymers |
| CN103183880A (en) * | 2011-12-30 | 2013-07-03 | 奇美实业股份有限公司 | Styrene-acrylonitrile-diene copolymer composition and molded article using same |
| CN103748159A (en) * | 2011-09-30 | 2014-04-23 | 株式会社可乐丽 | Rubber composition and tire |
| CN106009069A (en) * | 2011-09-30 | 2016-10-12 | 株式会社可乐丽 | Rubber composition and tire |
Family Cites Families (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| FR2577230B1 (en) * | 1985-02-08 | 1987-03-06 | Charbonnages Ste Chimique | NOVEL POLYMERIC RESIN COMPOSITIONS BASED ON ACRYLONITRILE-BUTADIENE-STYRENE WITH IMPROVED PROPERTIES |
| NL8702602A (en) * | 1987-11-02 | 1989-06-01 | Stamicarbon | THERMOPLASTIC POLYMER. |
-
1996
- 1996-08-23 CN CN96109456A patent/CN1051565C/en not_active Expired - Fee Related
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102164974B (en) * | 2008-09-04 | 2012-11-21 | 阿迈瑞斯公司 | Farnesene interpolymers |
| CN103748159A (en) * | 2011-09-30 | 2014-04-23 | 株式会社可乐丽 | Rubber composition and tire |
| CN103748159B (en) * | 2011-09-30 | 2016-01-20 | 株式会社可乐丽 | Rubber combination and tire |
| CN105646956A (en) * | 2011-09-30 | 2016-06-08 | 株式会社可乐丽 | Rubber composition and tire |
| CN106009069A (en) * | 2011-09-30 | 2016-10-12 | 株式会社可乐丽 | Rubber composition and tire |
| CN103183880A (en) * | 2011-12-30 | 2013-07-03 | 奇美实业股份有限公司 | Styrene-acrylonitrile-diene copolymer composition and molded article using same |
| CN103183880B (en) * | 2011-12-30 | 2015-06-10 | 奇美实业股份有限公司 | Styrene-acrylonitrile-diene copolymer composition and molded article using same |
Also Published As
| Publication number | Publication date |
|---|---|
| CN1051565C (en) | 2000-04-19 |
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