CN1068616C - Combined body of synthetic resin - Google Patents
Combined body of synthetic resin Download PDFInfo
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- CN1068616C CN1068616C CN94116305A CN94116305A CN1068616C CN 1068616 C CN1068616 C CN 1068616C CN 94116305 A CN94116305 A CN 94116305A CN 94116305 A CN94116305 A CN 94116305A CN 1068616 C CN1068616 C CN 1068616C
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Abstract
The present invention relates to a thermoplastic resin composition molding body and a synthetic resin composite body prepared from the thermoplastic resin composition molding body and a polyurethane foaming body, wherein the thermoplastic resin composition molding body is prepared from 50 to 99.5 wt. % of component (A) comprising styrene series resin of diene series rubber, 0.1 to 40 wt. % of component (B) of acrylic acid series rubber-like polymer and 0.1 to 40 wt. % of component (C) of vinyl monomer polymer of which the weight-average molecular weight is above 200 thousand, and the total amount of the components (B) and (C) is from 0.5 to 50 wt. %. The resin molding body is not easy to generate cracks of environmental stress, and the synthetic resin composite body is suitable for materials with the properties of heat insulation, shock resistance, sound insulation, etc.
Description
The present invention relates to a kind of by specific thermoplastic resin composition's the formed body and the synthetic resin complex of polyurethane foam anti-hydrofluoric ether that form, the tool excellence (Off ロ Application) performance and mechanical property, and a kind of adiabatic steel plate-synthetic resin complex of forming by this synthetic resin complex and steel plate.More particularly, this specific thermoplastic resin composition by the phenylethylene resin series that contains diene rubber, acrylic rubber shaped polymer, and weight-average molecular weight formed by the ethylene-based polymer more than 200,000.
With the ABS resin be representative, be well known by phenylethylene resin series that contains diene rubber and polyurethane foam body synthetic resin complex that form, that have heat-insulating property, and be widely used in as domestic refrigerator etc.This synthetic resin complex is in the presence of the ABS resin formed body, and making with polymeric polyisocyanate, polyvalent alcohol and whipping agent is that the mixture reaction of main component makes.And, as whipping agent, be extensive use of hydrofluoric ether, i.e. fluorine human relations (Off ロ Application).
Yet, in prepared synthetic resin complex like this, follow the cracking of environmental stress crack phenomenon on the ABS resin of the being everlasting formed body.Its reason can think, forms many slight void in the ABS resin formed body because of the stress that produces in the preparation process of synthetic resin complex makes, and the fluorine human relations meeting of using as the whipping agent of urethane is permeated in these microgaps and cut off polymer chain.
, now, use the specific fluorine human relations of fluorine human relations 11 grades so far to be identified as the material that damages the ozone layer as whipping agent, from the viewpoint of global environment protection, its manufacturing is ended in the industrial community plan.Therefore, people plan to use the fluorine human relations surrogate littler to the possibility of environmental disruption.Yet, give surely higher to the seepage force of resin as whipping agent compared with fluorine human relations 11 as the such chlorine human relations surrogate of fluorine human relations 141b (promptly 1,1-two chloro-1-fluoroethanes) and fluorine human relations 123 (promptly 1,1-two chloro-2,2,2-Halothane).
Thereby in the synthetic resin complex that fluorine human relations surrogate is made as whipping agent, the use of fluorine human relations 141b and fluorine human relations 123 more may make on the ABS resin formed body than the occasion of using fluorine human relations 11 and ftracture.
Therefore, also the someone has proposed to use content, the so-called high nitrile resin that significantly improves vinyl cyanide, and the refrigerator of anti-fluorohydrocarbon (fluorine human relations) performance of making the tool excellence is with the method (spy opens clear 62-228860 communique) of thermal insulation material.But the shortcoming of the resin that acrylonitrile content is high is: this resin strip yellow, and poor heat stability, and, adding man-hour in vacuum forming, the moulding product are in uneven thickness.
The present inventor is the problems referred to above of the synthetic resin complex that solves the relevant urethane foam that contains the styrene resin formed body of diene rubber and form, done to study intensively, the result, use contain diene rubber resins such as vinylbenzene, acrylic rubber shaped polymer, and weight-average molecular weight at the thermoplastic resin composition's of the ethylene-based polymer more than 200,000 formed body, make and polyurethane foaming body compound synthetic resin complex, thereby reached above-mentioned purpose.
That is, the present invention by the phenylethylene resin series that will contain diene rubber " composition (A) ", acrylic rubber shaped polymer composition, and weight-average molecular weight make compound resin composition and reach at thermoplastic resin composition's formed body of the component of polymer (C) of the vinyl monomer more than 200,000 and urethane foam.This thermoplastic resin composition contains (A) composition 50 one 99.5% (weight), (B) composition 0.1～40% (weight) and (C) composition 0.1-40% (weight), and (B) composition+(C) total amount of composition is 0.5～50% (weight).
At first, with regard to (A) of the present invention composition, the phenylethylene resin series that promptly contains diene rubber is done an explanation.The phenylethylene resin series composition (A) that contains diene rubber is made up of diene rubber constituent and resinous principle.As the diene rubber constituent, can use: divinyl, isoprene, dimethylbenzene divinyl, chloroprene, ring are defended the conjugate diene monomer of diene etc.; And 2, the homopolymer of non-conjugated diene hydrocarbon monomers such as 5-norbornadiene, 4-ethylidene norbornene, 1 etc.; Or with conjugated diene monomer or non-conjugated diene hydrocarbon monomer and vinylbenzene, alpha-methyl styrene, the aromatic vinyl class monomer of Vinyl toluene etc., vinyl cyanide, vinyl cyanide monomers such as methacrylonitrile, methyl acrylate, ethyl propenoate, butyl acrylate, ethyl propenoate, 2-EHA, acrylic ester monomers such as Octyl acrylate, methyl methacrylate, Jia Jibingxisuanyizhi, butyl methacrylate, N-Hexyl methacrylate, methacrylic acid 2-ethylhexyl, methyl acrylic ester monomers such as Octyl methacrylate, ethene, propylene, 1-butylene, iso-butylene, olefinic monomers such as 2-butylene, the maleic anhydride imines that contracts, the N-methyl maleic anhydride imines that contracts, the N-ethyl maleic anhydride imines that contracts, N-phenyl maleic anhydride maleic anhydrides such as the imines imide monomers that contracts that contracts, anhydrides monomers such as maleic anhydride, ethylene methacrylic ether, ethyl vinyl ether, propyl vinyl ether, the hexyl Vinyl Ether, the octadecyl Vinyl Ether, phenylvinyl ether, ethene ethers monomers such as glycidyl Vinyl Ether, methyl vinyl ketone, the copolymerization of vinyl ketones monomers such as phenyl vinyl ketone etc.
In addition, the diene rubber constituent also can be used the multipolymer of the multi-functional vinyl monomer of property in return.As this multi-functional vinyl monomer, can enumerate: Vinylstyrene, ethylene glycol dimethacrylate, the 1,3 butylene glycol dimethacrylate, the propylene glycol dimethacrylate, triallyl cyanurate, the cyamelide triallyl, allyl acrylate, allyl methacrylate(AMA), vinyl acrylate, the methacrylic vinyl acetate, glycidyl acrylate, glycidyl methacrylate etc.
Again, diene rubber constituent used in the composition (A) must have the skill of connecing active site, specifically is preferably in to have carbon-to-carbon double bond in the rubber constituent.
There is no particular restriction to use above-mentioned monomeric polymerization process, can use known technologies such as emulsion polymerization, solution polymerization.Again, composition (A) diene rubber constituent needs not to be single kind, also can be the mixture with the rubber constituent of other method polymeric more than two kinds.
In addition, (A) the diene rubber constituent in the composition is preferably between the 3-30% (weight) between 1-40% (weight).If this composition is less than 1% (weight), then shock strength is not enough, again, surpasses then rigidity deficiency of 40% (weight).
Monomer as the styrene resin composition that contains diene that constitutes composition of the present invention (A), must be as vinylbenzene, alpha-methyl styrene, Vinyl toluene, aromatic vinyl class monomer and vinyl cyanide such as t-butyl styrene, ethylene chloride class monomers such as methacrylonitrile, can only use these monomers, also can make this class monomer separately or and with following monomeric multipolymer: methyl acrylate, ethyl propenoate, butyl acrylate, ethyl propenoate, vinylformic acid α-ethylhexyl, acrylate-based monomer such as Octyl acrylate, methyl methacrylate, Jia Jibingxisuanyizhi, butyl methacrylate, N-Hexyl methacrylate, methacrylic acid α-ethylhexyl, methacrylate monomer such as methacrylic acid is sad, acrylamide, amides monomers such as Methacrylamide, vinylformic acid, methacrylic acid, unsaturated carboxylic acid class monomers such as methylene-succinic acid, ethene, propylene, 1-butylene, iso-butylene, olefin monomers such as alpha-butylene, the maleic anhydride imines that contracts, the N-methyl maleic anhydride imines that contracts, the N-ethyl maleic anhydride imines that contracts, the N-propyl group maleic anhydride imines that contracts, the N-cyclohexyl maleic anhydride imines that contracts, N-phenyl maleic anhydride maleic anhydrides such as the imines imines that contracts that contracts is a monomer, anhydrides monomers such as maleic anhydride, ethylene methacrylic ether, ethyl vinyl ether, propyl ethylene acid, the hexyl Vinyl Ether, the octadecyl Vinyl Ether, phenylvinyl ether, vinyl ether monomers such as Racemic glycidol Vinyl Ether, methyl vinyl ketone, vinyl ketones monomers such as phenyl vinyl ketone.
As mentioned above, (A) must contain aromatic vinyl monomer and vinyl cyanide monomer in the resin of composition, and the monomeric amount of vinyl cyanide is 20～50%.(weight) is then better, and the monomeric amount of vinyl cyanide is the then good especially of 25～45% (weight).Less than 20% (weight), then the anti-hydrofluoric ether performance of synthetic resin complex is not enough as its content, and surpassing 50% (weight) then can be owing to be heated and flavescence when forming process.
The used composition (A) of the present invention is made up of diene rubber and resin composition as mentioned above, but must have Grafting Structure on the interface of the diene rubber composition of granular texture and external phase resin.Know that such structure can make one of the monomer that constitutes resin composition portion or all carry out the so-called graft polymerization method of polymeric and reach in the presence of diene rubber composition, composition of the present invention (A) also can be made by known graft polymerization technique.
In order to regulate the containing ratio of diene rubber composition contained in (A) composition, also can in (A) composition, mix the resin composition that is polymerized separately.The resin composition that makes of polymerization needn't be identical with the resin composition with graft polymerization separately.For example, in the presence of polyhutadiene, making vinyl cyanide and vinylbenzene carry out graft polymerization makes in (A) composition, acrylonitritrile-styrene resin can be mixed with the resin composition, also can make polypropylene nitrile, vinylbenzene and alpha-methyl styrene separately and acrylonitrile-styrene-α-Jia Jibenyixigongjuwu of obtaining mixes mutually.
About the resin composition in (A) composition, address as preceding, when meaning in the presence of diene rubber composition polymerization, the polymkeric substance of graft polymerization and do not make the polymkeric substance of graft polymerization, and be to regulate diene rubber composition containing ratio blended polymkeric substance.
The phenylethylene resin series that contains diene rubber of used (A) composition among the present invention, can enumerate particularly: ABS (acrylonitrile-butadiene-styrene (ABS)) resin, heat-proof ABS (acrylonitrile-butadiene-alpha-methyl styrene) resin, AES (vinyl cyanide-EPDM-vinylbenzene) resin, MBAS (methyl methacrylate-butadiene-acrylonitrile-vinylbenzene) resin etc.
Below, just the acrylic ester rubbery polymer of used (B) composition is done an explanation among the present invention.As composition (B), for example can enumerate: methyl acrylate, ethyl propenoate, butyl acrylate, the vinylformic acid caproic acid, 2-EHA, cyclohexyl acrylate, Octyl acrylate, dodecylacrylate, the stearyl acrylate alcohol ester, vinylformic acid 2-ethoxy ethyl ester, the homopolymer or the multipolymer of acrylic ester monomers such as vinylformic acid 2-hydroxyl ethyl ester; And be selected from the monomeric homopolymer of methyl acrylic ester or the multipolymer of N-Hexyl methacrylate, methacrylic acid 2-ethylhexyl, Octyl methacrylate, methacrylic acid cetyl ester, lauryl methacrylate, decyl-octyl methacrylate, methacrylic acid stearyl, stearyl methacrylate and methacrylic acid pentyl ester etc.; And with a kind of of acrylate monomer and methyl methacrylate, Jia Jibingxisuanyizhi, propyl methacrylate, butyl methacrylate, cyclohexyl methacrylate, hydroxyethyl methylacrylate and above-mentioned methacrylate monomer etc. or copolymerization and getting more than 2 kinds.
Again, (B) the acrylic rubber shaped polymer in the composition uses when polymerization or does not use multi-functional vinyl monomer all right.This multi-functional vinyl monomer has; Ethylene glycol dimethacrylate, polyethylene glycol dimethacrylate, propylene glycol dimethacrylate, glycidyl methacrylate, Vinylstyrene, allyl acrylate, allyl methacrylate(AMA), vinyl acrylate, methacrylic vinyl acetate etc.
(B) composition of the present invention and second-order transition temperature must be preferably more than 10 ℃ below 20 ℃.When its second-order transition temperature surpasses 20 ℃, then its anti-hydrofluoric ether, and impact resistance variation.
Again, gel content must be below 70% in the present invention (B) composition, better should be below 50%.Gel content that should (B) composition is greater than 70% o'clock, the remarkable deterioration of its anti-hydrofluoric ether performance, and can not use.
The mensuration of the said gel content of the present invention: accurately weigh the about 1.0g of (B) composition (making Sog), put into the stainless steel wire netting of 400 purposes cage, immerse in the toluene of 100cc, 50 ℃ put 24 hours after, cylinder mould is proposed, the insoluble composition weight of at room temperature air-dry back weighing Sig calculates it by formula (2).
(Si/So)×100％ (Ⅰ)
(B) of the present invention composition makes has 8.4-9.8 (cal/cc
Solubility parameter in the scope.Better exist, this parameter should be at 8.6-9.6 (cal/cc
Scope.
When the solubility parameter of (B) composition less than 8.4 (cal/cc
The time, then the anti-fluorohydrocarbon performance of the synthetic resin complex of being made up of this thermoplastic resin composition's formed body and urethane foam is too poor and can not use.
In addition, the said solubility parameter of this specification sheets is used New York John wiley ﹠amp; Sons press distribution, Block ラ Application De ラ ッ プ and イ Application マ-ガ ッ ト in 1989 compile " polymer handbook " the 3rd edition VII, the solubility parameter value of being put down in writing on 519～559 pages, the solubleness reference number δ T of multipolymer can be calculated by the solubility parameter δ n and the weight ratio Wn substitution formula II thereof of the homopolymer of each (methyl) acrylate monomer from m kind (methyl) acrylate monomer that constitutes this multipolymer.
For example, the solubility parameter of the acrylic rubber shaped polymer that is made of n-butyl acrylate 80% (weight) and methyl methacrylate 20% (weight) is the solubility parameter 8.8 (cal/cc with n-butyl acrylate
And the solubility parameter 9.5 (cal/cc of methyl methacrylate
The substitution formula II calculates, and obtains 8.9 (cal/cc
There is no particular restriction to count the manufacture method of ester rubbery polymer about (B) of the present invention composition propylene, can use known technologies such as emulsion polymerization, suspension polymerization, solution polymerization, mass polymerization, but, wherein, with the manufacture method of emulsion polymerization industrial the most favourable.Because, in occasion of the present invention, contain (A) composition, (B) composition in preparation and (C) during this thermoplastic resin composition of composition, by the emulsion of (B) composition polymkeric substance and (C) the composition polymkeric substance the emulsification liquid-phase mixing and the polymeric blends that obtains mixes with composition (A) again, can obtain comparatively ideal thermoplastic resin composition, so it is suitable mixing with its emulsion state.
When preparation (B) composition polymkeric substance, the selection of acrylate monomer, or the selection of co-polymerized monomer can be carried out arbitrarily so long as can satisfy the scope that the present invention requires in second-order transition temperature, gel content and the solubility parameter of gained (B) composition polymkeric substance.
Below, just the vinyl monomer polymkeric substance of (C) composition is illustrated.
The object lesson that constitutes the vinyl monomer of (C) of the present invention composition has: vinylbenzene, alpha-methyl styrene, Vinyl toluene, aromatic vinyl class monomers such as t-butyl styrene; Vinyl cyanide, ethylene oxide class monomers such as methacrylonitrile; Vinyl cyanide, ethylene oxide class monomers such as methacrylonitrile; Methyl methacrylate, Jia Jibingxisuanyizhi, butyl methacrylate, N-Hexyl methacrylate, methacrylic acid 2-ethylhexyl, Octyl methacrylate, lauryl methacrylate, methyl acrylic ester monomers such as stearyl methacrylate; Methyl acrylate, ethyl propenoate, butyl acrylate, Ethyl acrylate, 2-EHA, vinylformic acid ring monooctyl ester, Octyl acrylate, dodecylacrylate, the stearyl acrylate alcohol ester, vinylformic acid 2-ethoxy ethyl ester, acrylic ester monomers such as vinylformic acid 2-hydroxyl ethyl ester; Acrylamide, acid amides such as Methacrylamide are monomer; Vinylformic acid, methacrylic acid, unsaturated carboxylic acid class monomers such as methylene-succinic acid; Ethene, propylene, 1-butylene, iso-butylene, olefin monomers such as 2-butylene; The maleic anhydride imines that contracts, the N-methyl maleic anhydride imines that contracts, the N-ethyl maleic anhydride imines that contracts, the N-propyl group maleic anhydride imines that contracts, the N-cyclohexyl maleic anhydride imines that contracts.The N-phenyl maleic anhydride imines that contracts, N-toluyl maleic anhydride maleic anhydrides such as the imines imines that contracts that contracts is a monomer; Anhydrides monomers such as maleic anhydride, divinyl, isoprene, amylene equiconjugate diolefinic monomer between chloro; Ethylene methacrylic ether, ethyl vinyl ether, ethene ethers monomers such as propyl vinyl ether; Methyl vinyl ketone, vinyl ketones monomers such as phenyl vinyl ketone; Vinyl pyridine etc., but be not limited to these monomers.
Composition (C) must have and is higher than 20 ℃ second-order transition temperature.Preferably be not less than 30 ℃.If second-order transition temperature is lower than 20 ℃, then thermoplastic resin composition's thermotolerance reduces, and does not reach the present invention's purpose.
Composition of the present invention (C) must have and is not less than 200,000 molecular-weight average, and the mensuration of molecular weight adopts polystyrene standard as checking and approving curve, and (GPC) carries out with gel permeation chromatography.Molecular-weight average is better should to be not less than 300,000.If molecular-weight average is lower than 200,000, the thickness of thermoplastic resin composition can produce non-uniform phenomenon when vacuum forming.
Have no particular limits for the method for preparing composition of the present invention (C) polymkeric substance.Can adopt conventional method for example letex polymerization, suspension polymerization, solution polymerization or mass polymerization.Yet it is, the most favourable with emulsion polymerization prepared from the viewpoint of industry.Because on the one hand, according to letex polymerization, easily in industrial manufacturing high molecular weight polymers; On the other hand, in the present invention, with (B) composition polymer emulsion with mix with (A) composition again after (C) composition polymer emulsion mixes mutually, can obtain the ideal thermoplastic resin composition, therefore be particularly suitable for mixing with its emulsion state.
When preparation composition of the present invention (C) polymkeric substance, vinyl monomer is arbitrarily, as long as the second-order transition temperature and the molecular-weight average of the composition that obtains (C) polymkeric substance satisfy requirement of the present invention.
In order to control the molecular weight of composition (C) polymkeric substance, can use chain-transfer agent.To the not special restriction of employed chain-transfer agent.For example, octyl mercaptan, decyl mercaptan, lauryl mercaptan, Thiovanic acid, ethyl thioglycolate, o-mercaptobenzoic acid ethyl ester, the halogen compound of tetracol phenixin etc.; Limonene or terpin diene, the nitro-compound of trinitrobenzene etc. or benzoquinones etc. all can use.
In the present invention, by being mixed with thermoplastic resin composition, make its composition that comprises 50～99.5% (weight) (A), the composition (C) of the composition of 1～40% (weight) (B) and 0.1～40% (weight), and wherein, the total amount of composition (B)+composition (C) is 0.5～50% (weight).Better, composition (A) is 60～98% (weight), and composition (B) is 0.6～28% (weight), and composition (C) is 0.6～28% (weight), and composition (B)+composition (C) is 2～40% (weight) for total amount.If the insufficient total amount 0.5% (weight) of composition (B)+composition (C), then the anti-fluorine human relations performance of thermoplastic resin composition's formed body of gained is not good, and when vacuum forming, thickness is easily inhomogeneous; And when this total amount surpasses 50% (weight), the rigidity of this formed body then, formability and thermotolerance are too poor and be not inconsistent use.
Composition (A), composition (B) and with the blending means of composition (C) there is no particular restriction, the mixing of powder attitude or two kinds of compositions of particulate state can make satisfactory thermoplastic resin composition.Mixing device has, for example Han Xieer mixing tank or cylinder etc.Have as the melting mixing device, for example, screw extrusion press, Bradley Bender mixing machine, Banbury, knead extrusion machine and mixing roll etc.
As a kind of better mixing, composition (A), (B) and step (C), preferably with composition (B) polymer emulsion and composition (C) polymer emulsion mixed after, separating obtained polymeric blends mixes with composition (A).
That is, with 20 to 80%, the polymer emulsified liquid of composition (C) of (weight) (solid composition meter of polymkeric substance) then separates obtaining polymer mixture with mixed mutually, mixes with composition (A) according to above-mentioned blending means then.More suitable is, above-mentioned composition emulsion is 30-70% (weight) (in the polymer solids composition), and composition (C) emulsion is 30-70% (weight) (a polymer solids composition meter).As composition B less than 20%, then anti-fluorine human relations are not good, and mobile obviously low; Surpass 80% (weight) as composition (B), itself and the intermiscibility variation of composition (A), forming composition is prone to exfoliated phenomenon, reaches surface-defects such as wave current line, and in addition, when vacuum forming, its thickness is also easily inhomogeneous.
With emulsion state mixing composition (B) emulsion and composition (C) emulsion the time, as with the manufactured composition of letex polymerization (B) polymkeric substance, or composition (C) polymkeric substance, then can directly use the emulsion polymerization liquid of letex polymerization gained, but in the occasion made from other polymerization, then must be earlier through the in addition emulsification of the resulting polymkeric substance of emulsification process.
There is no particular limitation for the emulsification method of polymkeric substance, can select a kind of ordinary method arbitrarily for use.For example, can adopt following method: after polymers soln and emulsifying agent and water are mixed together and stir, remove solvent; The micro mist that maybe will pulverize the polymkeric substance gained makes emulsion after stirring with emulsifying agent, water mixed together, polymkeric substance is pulverized the method that makes emulsion etc. in the presence of emulsifying agent and water.But and limit described method.
Be used for Emulgating polymers or composition (B) or (C) emulsifier type of the emulsion polymerization of polymkeric substance be not particularly limited, it can select anion surfactant arbitrarily, cats product, amphoterics becomes nonionogenic tenside.Yet it is best selecting anion surfactant for use.
Have no particular limits for the method for mixing above-mentioned composition (B) polymer emulsion and composition (C) polymer emulsion, mixing can be used for example fixed container type mixing tank, rotary container type mixing tank, and the static(al) mixing tank, devices such as line mixer carry out.
There is no particular restriction to isolate the method for polymeric blends from composition (B) polymer emulsion and composition (C) polymer emulsion mixture, for example, can adopt the method for following precipitation agent precipitate and separate: acids such as example hydrochloric acid, sulfuric acid, phosphoric acid or acetic acid; Ionogen such as sodium-chlor, calcium chloride, aluminum chloride, sodium sulfate, sal epsom etc.; The method of water-soluble polymer precipitation agent such as polyvinyl alcohol, polyoxyethylene glycol, polyethylene glycol-propylene glycol segmented copolymer, carboxymethyl cellulose etc., or adopt freezing breakdown of emulsion method, or in high-temperature gas, spray the emulsion breaking method.
Isolating polymkeric substance (body) mixture also can further carry out melting mixing in the melting mixing device from composition (B) and the mixed liquid of polymer emulsion (C).Spendable melting mixing device has Banbury, powerful mixing roll, and kneading machine is extruded mixing roll, roll-type mixing roll etc.
In addition, also can use the melting mixing machine of dewatering unit.In the case, the emulsion precipitation agent is added to kneading device continuously, mixes, breakdown of emulsion, dehydration, dry and melting mixing carries out in same kneading device continuously.
In thermoplastic resin complex body of the present invention, can mix other thermoplastic resin when needing, dispersion agent, lubricant, antioxidant, sterilant, pigment etc.
Synthetic resin complex of the present invention can with above-mentioned thermoplastic resin composition in advance forming process formed body in the presence of, with polyisocyanates, polyvalent alcohol and whipping agent is that the mixture reaction of main composition makes, but composition and the manufacture method to urethane foam do not have special restriction among the present invention.
Concrete row that can be used for preparing the polyisocyanates of urethane foam have: tolylene diisocyanate, adjacent tolylene diisocyanate, ditane-4,4-vulcabond, 1,3-xylylene vulcabond, 1,5-naphthalene diisocyanate and 1-methylcyclohexyl, 2,4-vulcabond etc.
The object lesson of polyvalent alcohol has 1,4-butyleneglycol, ethylene glycol, polyoxyethylene glycol, propylene glycol, polypropylene glycol, (oxygen ethene-oxypropylene) multipolymer, α, ω-polycaprolactone glycol and α, glycolss such as ω-polybutadiene diol, trivalent alcohol such as glycerol and TriMethylolPropane(TMP), tetramethylolmethane, Sorbitol Powder sucrose etc.In addition, also have oxyethane or propylene oxide and with the affixture of polyvalent alcohol.
Used whipping agent has, fluorine human relations 11, fluorine human relations 12, fluorine human relations 113, fluorine human relations 123, fluorine human relations 141b, methylene dichloride etc.
In preparation during polyurethane foaming body, the known use with water, organo-tin compound, tertiary amine to the catalyzer of representative as chemical foaming agent uses tensio-active agent etc. as bubble stabilizer.Relevant these methods have disclosed a lot of technical schemes, do not have special restriction for the polyurethane foam prescription among the present invention.
Below, illustrating in greater detail the present invention with embodiment, comparative example, part and % in the example all represent with weight.
At first, thermoplastic resin composition as the formed body material is described.
(1) composition (A)
To press mixed shown in the table 1 with the vinyl cyanide composition than different AS resins by ABS resin powder and vinylbenzene that polyhutadiene 50%, vinyl cyanide 15%, vinylbenzene 35% are formed, obtain (A) composition A-1, A-2 and A-4.Again, the ABS resin powder that to form by polyhutadiene 50%, vinyl cyanide 20%, vinylbenzene 30% and press mixed shown in the table 1 by the AS resin that vinylbenzene 60% and vinyl cyanide 40% are formed, get (A) composition A-3, and the GPC weight-average molecular weight of AS resin that is used for composition (A) is less than 200,000.
(2) composition (B)
The preparation of composition (B)
120 parts of pure water and 2 parts of Sodium dodecylbenzene sulfonatees are put into autoclave and under agitation are heated to 65 ℃.Contain the 0.005 part of ferrous sulfate heptahydrate that is dissolved in 10 parts of pure water, the aqueous solution of 0.01 part of tetrasodium ethylenediamine tetraacetate dihydrate and 0.3 part of formaldehyde sodium sulfoxylate dihydrate to wherein adding.
Then, 20% of 100 parts of monomer mixtures forming shown in the table 2 are added in the autoclave, add 2.5 part 0.2% persulfate aqueous solution initiated polymerization.In initiated polymerization, remaining above-mentioned monomer mixed solution was added wherein in 4 hours continuously.In addition, in initiated polymerization, the 0.05 part of Potassium Persulphate that is dissolved in 20 parts of pure water was added wherein in 6 hours continuously.After potassium persulfate solution adds, the cooling of the reactant in the autoclave to stop polyreaction, is obtained B-1 to B-6.The character of the composition that obtains (B) is shown in table 2 in the lump.
(3) composition (C)
The preparation of composition (C)
150 parts of pure water and 2 parts of potassium stearates are added in the autoclave, and under agitation are heated to 50 ℃.Be dissolved in 0.005 part of ferric sulfate heptahydrate in 10 parts of pure water, the aqueous solution of 0.01 part of tetrasodium ethylenediamine tetraacetate dihydrate and 0.3 part of formaldehyde sodium sulfoxylate dihydrate to wherein adding to contain.
100 parts and 0.08 part tert-dodecyl mercaptan of monomer mixed solution with component shown in the table 3 added in 4 hours continuously then.Simultaneously, in 6 hours, add 0.05 part continuously and be dissolved in 25 parts of Potassium Persulphates in the pure water.After monomer mixed solution adds, add 0.1 part of di-isopropylbenzene hydroperoxide.Make system be heated to 70 ℃, and continue to stir 2 hours, obtain C-1 to C-2 to finish polyreaction.Promptly get C-3 as adding 0.3 part of uncle-Dodecyl Mercaptan again.The character of gained composition (C) is shown in table 3 in the lump.
(4) based on composition (B) emulsion and composition (C) emulsion and the polymer mixture that obtains
Mix the preparation that composition (B) and emulsion (C) obtain polymer mixture (D)
Composition (B) polymer emulsion and composition (C) polymer emulsion are mixed with the emulsion state in ratio shown in the table 4 (with polymer solids content), 5 parts of calcium chloride dihydrates that are dissolved in 400 parts of pure water are heated to 80-95 ℃, and under agitation the above-mentioned emulsion mixture is added wherein, precipitate.The slurry that obtains filters, washes with water, and dry under 70 ℃ of conditions, obtain polymeric blends D-1-D-15,
And try to achieve the physicals of each sample with following method.
(1) second-order transition temperature
Drip component (B) or emulsion (C) and obtain solid in methyl alcohol, drying is tested its second-order transition temperature with DuPont910 differential scanning calorimeter and Du Pont990 thermal analyzer.
(2) weight-average molecular weight
Two GMH-6 type posts mensuration in upright arrangement of employing TOSOH corporate system HLC-802A type gel permeation chromatograph and the said firm's system.With a refractometer as detector, with tetrahydrofuran (THF) as solvent.
Composition (C) emulsion is separated out precipitation with methyl alcohol obtain solid as specimen.
(3) gel content
With composition (B) or (C) polymer emulsion be added dropwise to and obtain solid and drying in the methyl alcohol.Accurately the about 1.0g solid sample of weighing is measured and calculated for gel content with method noted earlier then.Yet the used solvent of composition (B) and composition (C) is different.Be composition (B) with butanone composition (C) use toluene.
(4) solubility parameter
The solubility parameter value of composition (B) acrylic rubber polymkeric substance is calculated it with preceding method.Embodiment 1
According to the usage ratio shown in the table 5, with the polymeric blends D-2 shown in A-160% shown in the table 1 and the table 4 (mix the C-1 polymeric blends of 60% B-1 polymkeric substance and 40% and get) 40% with emulsified state, carry out melting mixing at 230 ℃ with twin screw extruder, obtain the thermoplastic resin composition.This resin combination is infeeded T shape mould single screw extrusion machine, become the flat board of mean thickness 1mm 220 ℃ of following melt-processed, the flat board of gained is predrying, with pula Ge Xisite (プ ラ グ ア シ ス ト) compression vacuum shaper the planar surface temperature is controlled at about 160 ℃, carry out forming process.Obtain the box-like thermoplastic resin of uncovered as shown in Figure 1, its thickness is even.
The steel-molded body that above-mentioned formed body and uncovered as shown in Figure 1 is box-like cooperates, in the space around this two formed body, inject by 110 parts of tolylene diisocyanates, 100 parts of the annexation of methyl Racemic glycidol and propylene oxide (hydroxyl equivalent 110), 30 parts of fluorine human relations 141b, 3.5 parts in water, 0.4 part in lauric acid two-n-octyl tin, the mixture of 0.2 part of composition of tetramethyl guanidine, reacted 30 minutes down at 50 ℃, obtain synthetic resin complex.
The synthetic resin complex that obtains is placed in the thermostatic bath, repeat the cold cycling treatment of secondary-10 ℃/3 hours～40 ℃/3 hours.The molding that takes out thermoplastic resin composition from the resin composite body of cold cycling treatment test back examines, and does not see that any slight crack is arranged on this molding.
Synthetic resin complex is of a size of among Fig. 1: wide 175mm * long 256mm * high 30mm, polyurethane foam body thickness 5mm.
The ratio of components of evaluation result and resin combination is shown in table 5 in the lump.Embodiment 2～14
In the ratio shown in the table 5, (A) composition and polymeric blends (D) are done fusion with twin-screw extruder under 230 ℃ mixed, obtains the thermoplastic resin composition, respectively these thermoplastic resin compositions done evaluation as embodiment 1.The ratio of its evaluation result and resin combination is shown in table 5 in the lump.
Again, whether even about the evaluation of vacuum forming performance with thickness after the visual inspection vacuum forming, beat " 0 " in the time of evenly, beat when inhomogeneous " * ", be qualified with uniform moulding product.In addition, when making thermal cycling test, the formed body of heat-obtaining thermoplastic resin composition on the synthetic resin complex after the test is observed its outward appearance, does not have cracking, albinism, and the good person of outward appearance be " 0 ", cracking or albefaction part person conduct " * " are arranged.
Embodiment 15
Mix mutually as composition (C) as composition (B) and C-18% as composition (A) B-12% with A-180%, this mixture at 230 ℃, is made melting mixing with twin-screw extruder, obtain the thermoplastic resin composition.To the evaluation of these thermoplastic resin compositions' dos as embodiment 1, the thickness of the thermoplastic resin forming body that uncovered is box-like is even, again, does not also find slight crack on this thermoplastic resin forming body through thermal cycling test respectively.
Embodiment 16
As composition (A), B-224% mixes this mixture at 230 ℃ as composition (C) mutually as composition (B) and C-212%, makes melting mixing with twin-screw extruder, obtains the thermoplastic resin group and gives thing with A-180%.To the evaluation of these thermoplastic resin compositions' dos as embodiment 1, the thickness of the thermoplastic resin forming body that uncovered is box-like is even, again, does not also find slight crack on this thermoplastic resin forming body through thermal cycling test respectively.Comparative example 1-9
(A) composition and polymeric blends (D) are pressed ratio of components shown in the table 6, under 230 ℃, on twin-screw extruder, make melting mixing, obtain the thermoplastic resin composition, respectively to of the evaluation of these thermoplastic resin compositions' dos as embodiment 1.Its separately the ratio of evaluation result and resin combination be shown in table 6 in the lump.Comparative example 10
A-180% is as composition (A), and B-112% mixes this mixture at 230 ℃ as composition (C) mutually as composition (B) and C-38%, makes melting mixing with twin-screw extruder, obtains the thermoplastic resin composition.Respectively these thermoplastic resin compositions are done evaluation as embodiment 1, the thermoplastic resin forming body that uncovered is box-like in uneven thickness again, do not found slight crack through thermal cycling test on this thermoplastic resin formed body.
The formation of table 1 (A) composition monomer and rubbery polymer
| ABS resin | The AS resin | (A) composition of composition (weight %) | ||||||||
| ABS resin powder (weight %) | Combined amount (part) | AS resin (weight %) | Combined amount (part) | SM | AN | PBd | ||||
| SM | AN | PBd | SM | AN | ||||||
| A-1 | 35 | 15 | 50 | 30 | 70 | 30 | 70 | 59.5 | 25.5 | 15.0 |
| A-2 | 35 | 15 | 50 | 30 | 75 | 25 | 70 | 63.0 | 22.0 | 15.0 |
| A-3 | 30 | 20 | 50 | 30 | 60 | 40 | 70 | 51.0 | 34.0 | 15.0 |
| A-4 | 35 | 15 | 50 | 40 | 70 | 30 | 60 | 56.0 | 24.0 | 20.0 |
Monomeric composition of table 2 (B) composition and characteristic value
| N-BA part | Iso-BA (part) | EA (part) | MMA (part) | EDMA (part) | Second-order transition temperature (℃) | Gel content (%) | Solubility parameter (cal/cc) _ | |
| B-1 | 100 | 0 | 0 | 0 | 0 | -53 | 0.1 | 8.8 |
| B-2 | 0 | 80 | 19.5 | 0 | 0.5 | -42 | 1.0 | 9.1 |
| B-3 | 90 | 0 | 0 | 10 | 0 | -45 | 0.2 | 8.9 |
| B-4 | 80 | 0 | 0 | 20 | 0 | -35 | 0.1 | 8.9 |
| B-5 | 80 | 0 | 0 | 10 | 10 | -25 | 88.0 | 9.1 |
| B-6 | 30 | 0 | 0 | 70 | 0 | 52 | 3.0 | 9.3 |
Each monomer of table 3 (C) composition is formed and characteristic value
| SM (part) | AN (part) | MMA (part) | Weight-average molecular weight | Second-order transition temperature (℃) | |
| C-1 | 70 | 30 | 0 | 400,000 | 106 |
| C-2 | 60 | 30 | 10 | 370,000 | 102 |
| C-3 | 70 | 30 | 0 | 100,000 | 106 |
Table 4 polymer mixture (D)
| Polymer mixture | (D) composition | |||
| (B) composition (weight %) | (C) composition (weight %) | |||
| D-1 | B-1 | 80 | C-1 | 20 |
| D-2 | B-1 | 60 | C-1 | 40 |
| D-3 | B-1 | 40 | C-1 | 60 |
| D-4 | B-1 | 20 | C-1 | 80 |
| D-5 | B-2 | 60 | C-1 | 40 |
| D-6 | B-3 | 60 | C-1 | 40 |
| D-7 | B-4 | 60 | C-1 | 40 |
| D-8 | B-1 | 60 | C-2 | 40 |
| D-9 | B-1 | 100 | - | 0 |
| D-10 | B-4 | 100 | - | 0 |
| D-11 | - | 0 | C-1 | 100 |
| D-12 | B-1 | 60 | C-3 | 40 |
| D-13 | B-2 | 60 | C-3 | 40 |
| D-14 | B-5 | 60 | C-1 | 40 |
| D-15 | B-6 | 60 | C-1 | 40 |
The ratio and the evaluation result of table 5 thermoplastic resin composition (A) composition and polymer mixture (D)
| Embodiment | (A) composition (weight %) | Polymer mixture (D) (weight %) | Vacuum formed product thickness is estimated | Thermal cycling is handled and is estimated | ||
| Embodiment 1 | A-1 | 60 | D-2 | 40 | ○ | ○ |
| Embodiment 2 | A-1 | 80 | D-2 | 20 | ○ | ○ |
| Embodiment 3 | A-1 | 90 | D-2 | 10 | ○ | ○ |
| Embodiment 4 | A-1 | 95 | D-2 | 5 | ○ | ○ |
| Embodiment 5 | A-1 | 80 | D-1 | 20 | ○ | ○ |
| Embodiment 6 | A-1 | 80 | D-3 | 20 | ○ | ○ |
| Embodiment 7 | A-1 | 89 | D-4 | 11 | ○ | ○ |
| Embodiment 8 | A-1 | 80 | D-5 | 20 | ○ | ○ |
| Embodiment 9 | A-1 | 80 | D-6 | 20 | ○ | ○ |
| Embodiment 10 | A-1 | 80 | D-7 | 20 | ○ | ○ |
| Embodiment 11 | A-1 | 80 | D-8 | 20 | ○ | ○ |
| Embodiment 12 | A-2 | 80 | D-2 | 20 | ○ | ○ |
| Embodiment 13 | A-3 | 80 | D-2 | 20 | ○ | ○ |
| Embodiment 14 | A-4 | 80 | D-2 | 20 | ○ | ○ |
Vacuum formed product thickness; Zero evenly, * inhomogeneous
Thermal cycling is handled and is estimated; Zero flawless, * slight crack arranged
The ratio and the evaluation result of table 6 thermoplastic resin composition (A) composition and polymer mixture (D)
| Comparative example | (A) composition (weight %) | Polymer mixture (D) (weight %) | Vacuum formed product thickness is estimated | Thermal cycling is handled and is estimated | ||
| Comparative example 1 | A-1 | 100 | - | 0 | ○ | × |
| Comparative example 2 | A-2 | 100 | - | 0 | ○ | × |
| Comparative example 3 | A-1 | 80 | D-9 | 20 | × | ○ |
| Comparative example 4 | A-1 | 80 | D-10 | 20 | × | ○ |
| Comparative example 5 | A-1 | 80 | D-11 | 20 | ○ | × |
| Comparative example 6 | A-1 | 80 | D-12 | 20 | × | ○ |
| Comparative example 7 | A-1 | 80 | D-13 | 20 | × | ○ |
| Comparative example 8 | A-1 | 80 | D-14 | 20 | ○ | × |
| Comparative example 9 | A-1 | 80 | D-15 | 20 | ○ | × |
Vacuum formed product thickness; Zero evenly, * inhomogeneous
Thermal cycling handle to be estimated: zero flawless, * slight crack arranged
The monomer mark is expressed as follows in each table:
SM is a vinylbenzene, and AN is that vinyl cyanide, pBd are polyhutadiene, and n-BA is a n-butyl acrylate, and iso-BA is an isobutyl acrylate, and EA is an ethyl propenoate, and MMA is a methyl methacrylate, and EDMA is an Ethylene glycol dimethacrylate.
As mentioned above, by the phenylethylene resin series that contains diene rubber, acrylic rubber shaped polymer and weight-average molecular weight are more than 200,000, the thermoplastic resin composition that ethylene-based polymer is formed, its vacuum formability is good, again, and the synthetic resin complex of forming by this thermoplastic resin composition's formed body and polyurethane foaming body, can be suppressed at that cracked takes place under the environment for use of cold cycling etc., thereby can be used for thermal insulation material, anti-seismic material and sound-proof material etc. effectively.
Fig. 1 (a) is depicted as the sectional view of thermoplastic resin composition's formed body;
Fig. 1 (b) is depicted as the top view of synthetic resin complex;
Fig. 1 (c) is depicted as the A-A ' sectional view of above-mentioned (b) synthetic resin complex.
Among the figure, 1 is thermoplastic resin composition's formed body, and 2 is steel-molded body, and 3 is polyurethane foaming body.
Claims (3)
1. synthetic resin complex of forming by thermoplastic resin composition's formed body and polyurethane foaming body, described resin combination contains following compositions (A), (B) reaches (C), described each component proportions is composition (A) 50-99.5% (weight), composition (B) 0.1-40% (weight) and composition (C) 0.1-40% (weight), and the total amount of composition (B)+composition (C) is 0.5-50% (weight);
Composition (A) is the composition of a polymkeric substance, the combination system of described polymkeric substance by the mixed grafting polymkeric substance, and, the polymkeric substance of being made up of aromatic vinyl monomer that constitutes resinous principle and vinyl cyanide monomer when needing forms; Described graftomer ties up under the existence of diene series rubber shaped polymer, will constitute aromatic vinyl monomer, the vinyl cyanide monomer of resinous principle and can obtain with other vinyl monomer polymerizations of described monomer copolymerization when needing; And described polymer composition is made up of diene series rubber composition 1-40% (weight) and resinous principle 60-99% (weight); Described composition (A) is one in described resinous principle, and containing the vinyl cyanide monomer content again is the styrene resin of the diene series rubber of 20-50% (weight);
Composition (B) is an acrylic rubber shaped polymer, and described acrylic rubber shaped polymer system will be selected from more than one monomer and the multi-functional vinyl monomer polymerization when needing and getting of acrylate monomer and methacrylate monomer;
Composition (C) is a vinyl monomer polymkeric substance, the polymkeric substance that described vinyl monomer polymer system can obtain with other vinyl monomer polymerizations of its copolymerization with aromatic vinyl monomer, vinyl cyanide monomer and when needing, and the weight-average molecular weight of described polymkeric substance is more than 200,000.
2. synthetic resin complex as claimed in claim 1 is characterized in that, described composition (A) is selected from one or two or more kinds of ABS resin, heat-resisting ABS resin, AES resin and MBAS resin.
3. synthetic resin complex as claimed in claim 1 is characterized in that, described composition (C) is the polymkeric substance of being made up of vinylbenzene and vinyl cyanide, or, the polymkeric substance of forming by vinylbenzene, vinyl cyanide and methacrylic ester.
Priority Applications (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP19255494A JP3487646B2 (en) | 1994-08-16 | 1994-08-16 | Synthetic resin composite |
| CN94116305A CN1068616C (en) | 1994-08-16 | 1994-09-15 | Combined body of synthetic resin |
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP19255494A JP3487646B2 (en) | 1994-08-16 | 1994-08-16 | Synthetic resin composite |
| CN94116305A CN1068616C (en) | 1994-08-16 | 1994-09-15 | Combined body of synthetic resin |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1118792A CN1118792A (en) | 1996-03-20 |
| CN1068616C true CN1068616C (en) | 2001-07-18 |
Family
ID=37076193
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN94116305A Expired - Lifetime CN1068616C (en) | 1994-08-16 | 1994-09-15 | Combined body of synthetic resin |
Country Status (2)
| Country | Link |
|---|---|
| JP (1) | JP3487646B2 (en) |
| CN (1) | CN1068616C (en) |
Families Citing this family (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE19924092A1 (en) * | 1999-05-26 | 2000-11-30 | Bayer Ag | Adhesion-stable composite material made of polyurethane and another thermoplastic material, a process for its production and its use in motor vehicles |
| JP2004293313A (en) | 2003-03-25 | 2004-10-21 | Hitachi Unisia Automotive Ltd | Fuel injection valve |
| CN107446299B (en) * | 2016-05-31 | 2019-11-19 | 金发科技股份有限公司 | A kind of refrigeration equipment environmental protection and energy saving structure sheaf and its application |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS6228409A (en) * | 1985-07-26 | 1987-02-06 | Teijin Ltd | Antistatic fiber and production thereof |
| JPS6256619A (en) * | 1985-09-03 | 1987-03-12 | Hoshizaki Electric Co Ltd | Bearing structure |
| EP0483832A2 (en) * | 1990-11-02 | 1992-05-06 | Monsanto Kasei Company | Thermoplastic resin composition |
-
1994
- 1994-08-16 JP JP19255494A patent/JP3487646B2/en not_active Expired - Fee Related
- 1994-09-15 CN CN94116305A patent/CN1068616C/en not_active Expired - Lifetime
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS6228409A (en) * | 1985-07-26 | 1987-02-06 | Teijin Ltd | Antistatic fiber and production thereof |
| JPS6256619A (en) * | 1985-09-03 | 1987-03-12 | Hoshizaki Electric Co Ltd | Bearing structure |
| EP0483832A2 (en) * | 1990-11-02 | 1992-05-06 | Monsanto Kasei Company | Thermoplastic resin composition |
Also Published As
| Publication number | Publication date |
|---|---|
| JP3487646B2 (en) | 2004-01-19 |
| JPH0852831A (en) | 1996-02-27 |
| CN1118792A (en) | 1996-03-20 |
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