CN100549088C - Have improved thermotolerance, welding strength, chemical resistant properties, shock strength, prolongation and wettable Plastic Resin composition - Google Patents

Have improved thermotolerance, welding strength, chemical resistant properties, shock strength, prolongation and wettable Plastic Resin composition Download PDF

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CN100549088C
CN100549088C CNB2005800093791A CN200580009379A CN100549088C CN 100549088 C CN100549088 C CN 100549088C CN B2005800093791 A CNB2005800093791 A CN B2005800093791A CN 200580009379 A CN200580009379 A CN 200580009379A CN 100549088 C CN100549088 C CN 100549088C
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CN1934189A (en
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李载煜
蔡承勋
车在赫
金成龙
李灿弘
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LG Corp
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    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L55/00—Compositions of homopolymers or copolymers, obtained by polymerisation reactions only involving carbon-to-carbon unsaturated bonds, not provided for in groups C08L23/00 - C08L53/00
    • C08L55/02—ABS [Acrylonitrile-Butadiene-Styrene] polymers
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    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L25/00—Compositions of, homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an aromatic carbocyclic ring; Compositions of derivatives of such polymers
    • C08L25/02—Homopolymers or copolymers of hydrocarbons
    • C08L25/04—Homopolymers or copolymers of styrene
    • C08L25/08—Copolymers of styrene
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    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L33/00—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides or nitriles thereof; Compositions of derivatives of such polymers
    • C08L33/04—Homopolymers or copolymers of esters
    • C08L33/06—Homopolymers or copolymers of esters of esters containing only carbon, hydrogen and oxygen, which oxygen atoms are present only as part of the carboxyl radical
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    • C08L51/00—Compositions of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers
    • C08L51/06—Compositions of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers grafted on to homopolymers or copolymers of aliphatic hydrocarbons containing only one carbon-to-carbon double bond
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    • C08L79/00—Compositions of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing nitrogen with or without oxygen or carbon only, not provided for in groups C08L61/00 - C08L77/00
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    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
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Abstract

The invention provides the thermoplastic resin composition.The heat-proof ABS thermoplastic resin composition who comprises the multipolymer that grafted ABS polymkeric substance, α-Jia Jibenyixigongjuwu, imines replace and be used to improve the additive of prolongation property and shock strength is being excellent aspect welding strength, chemical resistant properties, shock strength and the prolongation.The thermoplastic resin composition who comprises grafted ABS polymkeric substance, α-Jia Jibenyixigongjuwu and be used to improve wettable additive is being excellent aspect welding strength and the wetting properties.

Description

Have improved thermotolerance, welding strength, chemical resistant properties, shock strength, prolongation and wettable Plastic Resin composition
Technical field
The present invention relates to a kind of thermoplastic resin composition, more specifically, relate to a kind of have improved welding strength, chemical resistant properties, shock strength, prolongation and wettable heat resistant propylene nitrile-butadiene-styrene (ABS) resin combination.
Background technology
Usually, heat resistant propylene nitrile-butadiene-styrene (ABS) resin with excellent shock resistance, processibility, chemical resistant properties etc. is as the inside and outside material of motor vehicle etc., and part is used for the Electrical and Electronic equipment as office equipment and home appliance.Under the situation of ABS, need a kind of high performance heat resistant resin with superior thermotolerance and multiple post-treatment character as the inside and outside material of motor vehicle.
In order to give described ABS resin thermotolerance, by mixing heat-resistant copolymer and of the method widespread use of grafted ABS polymkeric substance to prepare heat-proof ABS.That is to say, known in the art, a kind of method for preparing heat-resisting ABS resin, the vinylbenzene (United States Patent (USP) the 3rd, 111, No. 501) that wherein replaces part or the total amount be used to prepare heat-resistant copolymer with alpha-methyl styrene with good heat resistance, a kind of preparation contains the method (European patent the 0th of the heat-resisting ABS resin of acrylamide compound, 330, No. 038), or the like.
According to United States Patent (USP) the 3rd, 111, No. 501, in the preparation of heat-resisting ABS resin, replace the vinylbenzene of part or total amount with alpha-methyl styrene with good heat resistance.Yet because α-vinylbenzene has the speed of reaction low than other monomers, a large amount of monomer residues causes low yield and poor shock strength and thermotolerance.When needs were used for the better thermotolerance of industrial application, the multipolymer that mixes the imines replacement was with the preparation heat-resisting ABS resin.By adopting the N-phenylmaleimide (United States Patent (USP) the 4th, 567, No. 233) in the preparation of thermotolerance toughener or adopting N-Chloro-O-Phenyl maleimide or allyl group, alkyl or ring-type substituent, and prepare this heat-proof ABS (United States Patent (USP) the 3rd, 652, No. 726 and the 5th, 726, No. 265).Yet these methods have the high shortcoming of manufacturing cost.
Consider thermotolerance and cost effectiveness, ABS is that the multipolymer that heat-resistant copolymer and imines replace mixes with above-mentioned two kinds of materials.When mixing these materials, the consistency between two kinds of materials is poor, has therefore weakened shock strength and prolongation property.
Heat-proof ABS as interior of motor vehicles and outer material often carries out the post-treatment processing.The representative example of described last handling process is a spraying process.In described spraying process, when resin does not have the chemical solvents affinity, cause surface imperfection as pin hole or spraying stain.When the chemical resistant properties difference of resin, produce the spraying crack.
And then when resin did not have the chemical solvents affinity, described spraying process need carry out repeatedly, particularly caused chemical solvents waste and workman's discomfort.In addition, the thick coating of chemical solvents causes its poor coatingsurface in dry back.
Particularly, except thermotolerance and spray characteristics, the thermoplastic resin composition who is used as the automotive lamp cover material needs good welding strength.Described welding strength for when the cross section of heating moldings with the welding of other moldingss, required a kind of character when obtaining whole goods thus.When separating with hot plate, the face of weld of described moldings should be clearly.Yet when separating with hot plate, the thermoplastic resin composition that used most of rubber is strengthened in the prior art produces a lot of thorns in its face of weld usually, needs additional procedure to remove deburring, and has reduced productivity.
Summary of the invention
The invention provides a kind of thermoplastic resin composition with improved thermotolerance, welding strength, chemical resistant properties, shock strength and prolongation.
The present invention also provides a kind of have improved welding strength and wettable thermoplastic resin composition.
According to a technical scheme of the present invention, provide a kind of thermoplastic resin composition who comprises the multipolymer that grafted ABS polymkeric substance, α-Jia Jibenyixigongjuwu, imines replace and be used to improve the additive of prolongation property and shock strength.
Described thermoplastic resin composition can comprise the multipolymer that the imines of α-Jia Jibenyixigongjuwu, 10～30 weight parts of grafted ABS polymkeric substance, 20～80 weight parts of 20～40 weight parts replaces and the additive that is used to improve prolongation property and shock strength of 1～10 weight part.
Described thermoplastic resin composition can comprise the multipolymer that the imines of α-Jia Jibenyixigongjuwu, 10～30 weight parts of grafted ABS polymkeric substance, 20～40 weight parts of 20～40 weight parts replaces and the additive that is used to improve prolongation property and shock strength of 1～10 weight part.Can be by the median size of copolymerization 10～40 weight parts And gel content is that 80～90% content of polybutadiene rubber latex (small grain size rubber latex), the median size of 15～30 weight parts are
Figure C20058000937900062
And gel content is 80～90% content of polybutadiene rubber latex (volume particle size rubber latex), the aromatic ethenyl compound of 15～30 weight parts and the described grafted ABS polymkeric substance of vinyl cyanide compound of 10～25 weight parts.
Described aromatic ethenyl compound can be selected from the group that comprises vinylbenzene, alpha-methyl styrene and p-Vinyl toluene.
Described vinyl cyanide compound can be selected from the group that comprises vinyl cyanide, methacrylonitrile and ethyl acrylonitrile.
Described α-Jia Jibenyixigongjuwu can be by copolymerization alpha-methyl styrene and vinyl cyanide preparation.
Described α-Jia Jibenyixigongjuwu can prepare by the alpha-methyl styrene of copolymerization 50～80 weight parts and the vinyl cyanide of 20～50 weight parts.
The described additive that is used to improve prolongation property and shock strength can be the multipolymer of polymethylmethacrylate (PMMA) multipolymer, vinylbenzene and maleic anhydride or the multipolymer of α-Jia Jibenyixigongjuwu and maleic anhydride.
Described PMMA multipolymer can be selected from the group of the graft copolymer (PMMA-g-VA) of the graft copolymer (PMMA-g-EA) of graft copolymer (PMMA-g-MAH), methyl methacrylate and ethyl propenoate of the graft copolymer (PMMA-g-GMA), methyl methacrylate and the maleic anhydride that comprise methyl methacrylate and glycidyl methacrylate and methyl methacrylate and vinyl-acetic ester.
Described thermoplastic resin composition can comprise at least a additive that is selected from the group that comprises antioxidant, stablizer and lubricant in addition.
Based on the described thermoplastic resin composition of 100 weight parts, the content of antioxidant can be 0.1～5 weight part, and the content of stablizer can be 0.1～5 weight part, and the content of lubricant can be 0.1～10 weight part.
According to another technical scheme of the present invention, a kind of comprise grafted ABS polymkeric substance, α-Jia Jibenyixigongjuwu and the thermoplastic resin composition who is used to improve wettable additive are provided.
What described thermoplastic resin composition can comprise the α-Jia Jibenyixigongjuwu of grafted ABS polymkeric substance, 20～80 weight parts of 20～40 weight parts and 0.1～5 weight part is used to improve wettable additive.
Describedly be used to improve wettable additive and can be and be selected from least a of the group that comprises polypropylene glycol, polyoxyethylene glycol and segmented copolymer thereof.
Describedly be used to improve wettable additive and can have 500～5,000 weight-average molecular weight.
Described thermoplastic resin composition can comprise the multipolymer that imines replaces in addition and be used to improve the additive of prolongation property and shock strength.
Described thermoplastic resin composition can comprise multipolymer that the imines of α-Jia Jibenyixigongjuwu, 10～30 weight parts of grafted ABS polymkeric substance, 20～40 weight parts of 20～40 weight parts replaces, 1～10 weight part be used to improve the additive of prolongation property and shock strength and 0.1～5 weight part be used to improve wettable additive.
Thermoplastic resin according to the present invention is being excellent aspect welding strength, chemical resistant properties, shock strength, prolongation and wetting properties and the thermotolerance.
Embodiment
The present invention is with following detailed description.
A kind of thermoplastic resin composition according to embodiment of the present invention comprises multipolymer that grafted ABS polymkeric substance, α-Jia Jibenyixigongjuwu, imines replace and the additive that is used to improve prolongation property and shock strength, and has excellent thermotolerance, welding strength, chemical resistant properties, shock strength and prolongation.
Preferably, described thermoplastic resin composition comprises the multipolymer that the imines of α-Jia Jibenyixigongjuwu, 10～30 weight parts of grafted ABS polymkeric substance, 20～80 weight parts of 20～40 weight parts replaces and the additive that is used to improve prolongation property and shock strength of 1～10 weight part.
More preferably, described thermoplastic resin composition comprises the multipolymer that the imines of α-Jia Jibenyixigongjuwu, 10～30 weight parts of grafted ABS polymkeric substance, 20～40 weight parts of 20～40 weight parts replaces and the additive that is used to improve prolongation property and shock strength of 1～10 weight part.
Based on the grafting AB8 polymkeric substance of 100 weight parts, the content of described α-Jia Jibenyixigongjuwu can be 50～400 weight parts.When the content of described α-Jia Jibenyixigongjuwu during less than 50 weight parts, shock strength, prolongation property or chemical resistant properties are poor.When the content of described α-Jia Jibenyixigongjuwu during greater than 400 weight parts, tensile strength, thermotolerance, flowability and gloss difference.
Based on the grafted ABS polymkeric substance of 100 weight parts, the content of the multipolymer that described imines replaces can be 25～150 weight parts.The content of the multipolymer that replaces when described imines is not in above-mentioned scope the time, and thermotolerance and mechanical property weaken.
Based on the grafted ABS polymkeric substance of 100 weight parts, the content of additive that is used to improve prolongation property and shock strength can be 2.5～50 weight parts.When described content of additive during less than 2.5 weight parts, prolongation property and shock strength are poor.When described content of additive during greater than 50 weight parts, poor heat resistance.
Each component of described thermoplastic resin composition now will be described in further detail.
The grafted ABS polymkeric substance
Can be by the median size of copolymerization 10～40 weight parts
Figure C20058000937900101
And gel content is that 80～90% content of polybutadiene rubber latex, the median size of 15～30 weight parts are
Figure C20058000937900102
And gel content is 80～90% content of polybutadiene rubber latex, the aromatic ethenyl compound of 15～30 weight parts and the described grafted ABS polymkeric substance of vinyl cyanide compound of 10～25 weight parts.
When independent use has
Figure C20058000937900103
The rubber latex of median size the time, surface luster improves, but shock strength significantly reduces.When independent use has
Figure C20058000937900104
The rubber latex of median size the time, shock strength improves, but surface luster is significantly reduced.Owing to these reasons, use the mixture of content of polybutadiene rubber latex with different-grain diameter.For fear of these shortcomings, keep the character of each rubber latex, and improve tensile strength, preferred use has mean particle size by mixing and is
Figure C20058000937900105
Rubber latex (small grain size rubber latex) and have median size and be
Figure C20058000937900106
The grafted ABS resin of rubber latex (volume particle size rubber latex) preparation.In this case, based on the small grain size rubber latex of 100 weight parts, the content of volume particle size rubber latex can be 37.5～300 weight parts.When the content of volume particle size rubber latex during, produce chain line (string) less than 37.5 weight parts.When the content of volume particle size rubber latex during greater than 300 weight parts, the mobile reduction.
Preparation small grain size rubber latex, thereafter by with acid with the small grain size rubber latex in conjunction with preparation volume particle size rubber latex.
Being used for the median size of rubber latex of preparation of described grafted ABS polymkeric substance and gel content has a significant impact the shock strength and the processibility tool of resin.Usually, when the particle diameter of rubber latex diminished, shock resistance and processibility reduced, and when particle diameter became big, shock resistance improved.In addition, when the gel content step-down, be aggregated on the side of rubber latex and carry out in monomeric swelling state, therefore, when the appearance particle diameter became big, shock strength improved.Yet the gel content of rubber latex is big, and when particle diameter was big, percentage of grafting reduced.Percentage of grafting is the character of impact polymer significantly.If percentage of grafting reduces, then have the not naked rubber latex of grafted, so thermostability weakens.
In the present invention, the following mensuration of gel content, exponent of expansion, median size and percentage of grafting.
＜gel content and exponent of expansion 〉
With diluted acid or metal-salt curing rubber latex, wash this cured article and in 60 ℃ vacuum drying oven dry 24 hours.The block rubber of gained is cut into pieces with scissors, and the 1g sheet rubber is joined in the 100g toluene, at room temperature stored 48 hours in the darkroom then.Resultant is separated into colloidal sol and gel, measures gel content and exponent of expansion according to following formula then:
Gel content (%)=insoluble part (gel) weight/sample heavy * 100
Exponent of expansion=expansion gel weight/gel is heavy
＜median size 〉
Adopt Nicomp (model: 370HPL) measure by dynamic laser scattering method (dynamiclaser-light scattering method).
＜percentage of grafting 〉
Graftomer is solidified, wash also dry to obtain powdery polymer.This powdery polymer of 2g joins in the 300ml acetone, stirs 24 hours.Adopt ultracentrifuge to separate this solution.Then, isolating acetone soln is dropped on the methyl alcohol, to obtain not grafting part.Drying and this not grafting part of weighing.Calculate percentage of grafting according to following formula:
Percentage of grafting (%)=grafted monomer weight/rubber heavy * 100
Hereinafter, by the preparation process that is divided into the small grain size rubber latex, the preparation process and the graft copolymerization step of volume particle size rubber latex, explain the preparation process of grafted ABS copolymer resin in detail.
The preparation of＜small grain size rubber latex 〉
Being used for small grain size rubber latex of the present invention is a kind of conjugated diolefin polymer, and preferably has
Figure C20058000937900121
Median size and 80～90% gel content.When this gel content greater than 90% the time, shock strength reduces.When this gel content less than 70% the time, thermostability reduces.
The molecular weight regulator of the polymerization starter of the conjugate diene monomer by in reactor, adding 100 weight parts altogether, the emulsifying agent of 1～4 weight part, 0.1～0.6 weight part, the ionogen of 0.1～1.0 weight part, 0.1～0.5 weight part, 90～130 weight parts remove deionized water, and under 50～65 ℃, reacted 7～12 hours, once all add the molecular weight regulator of 0.05～1.2 weight part altogether then in addition, and under 55～70 ℃, reacted 5～15 hours preparation small grain size rubber latex.
Described emulsifying agent is alkali salt of alkylaryl sulfonate, alkali metal alkyl sulfate, sulfonated alkyl ester, soap, rosinate or the like, and the mixture that they can be independent or two or more uses.
Described polymerization starter can be water-soluble persulphate, superoxide, redox compound or fat-soluble polymerization starter.Described water-soluble persulphate can be sodium or potassium persulphate.Described fat-soluble polymerization starter can be cumene hydroperoxide hydrogen thing, diisopropylbenzenehydroperoxide thing, azo Di-Isobutyl nitrile, tertbutyl peroxide thing, Pa Lameisa (paramethane) hydroperoxide, benzoyl peroxide or the like, and the mixture that they can be independent or two or more uses.
Described ionogen can independent or two or more mixing use KCl, NaCl, KHCO 3, NaHCO 3, K 2CO 3, Na 2CO 3, KHSO 3, NaHSO 3, K 4P 2O 7, K 3PO 4, Na 3PO 4, K 2HPO 4And Na 2HPO 4Or the like.
Described molecular weight regulator is mercaptan series preferably.
Polymerization temperature is very important for the gel content and the exponent of expansion of control rubber latex, wherein should consider the selection of initiator.
The preparation of＜volume particle size rubber latex (in conjunction with the small grain size rubber latex) 〉
Usually, because the median size of volume particle size rubber latex provides HI high impact character in thermoplastic resin, so its preparation is very important.In order to satisfy the physical properties among the present invention, required median size preferably exists
Figure C20058000937900131
In the scope.
Be prepared as follows described volume particle size rubber latex.
2.5～4.5 weight part acetic acid solutions are slowly joined 100 weight part particle diameters is
Figure C20058000937900132
Figure C20058000937900133
And gel content is 80～90% small grain size rubber latex, and stirs 1 hour, and to improve granularity, combination prepares the volume particle size rubber latex by stopping to stir then, so that it has Particle diameter and 80～90% gel content.
＜graft polymerization 〉
By aromatic ethenyl compound and vinyl cyanide and by the small grain size rubber latex of method for preparing and the graft copolymerization of volume particle size rubber latex, preparation grafted ABS multipolymer.
That is to say, the aromatic ethenyl compound of 15～40 weight parts, the vinyl cyanide of 5～20 weight parts, the emulsifying agent of 0.2～0.6 weight part, the molecular weight regulator of 0.2～0.6 weight part and the polymerization starter of 0.1～0.5 weight part etc. are added the conjugated diene rubber latex of 40～70 weight parts, and carry out graft copolymerization with preparation grafted ABS multipolymer.When grafting, preferred 45～80 ℃ of polymerization temperature, and preferred 3～5 hours of polymerization time.
The method that adds each component can be used once all addition methods, the rapid addition method of multistep and continuous addition method.In order to improve percentage of grafting and the formation of solid matter to be minimized, preferred rapid addition method of multistep and continuous addition method.
Described grafted ABS polymkeric substance can prepare by the following method, comprise step: the mixture, the aromatic ethenyl compound of 5～10 weight parts, the vinyl cyanide of 5～10 weight parts, the emulsifying agent of 0.1～0.5 weight part and the deionized water of 50～80 weight parts that (A) add two kinds of content of polybutadiene rubber latex of 40～60 weight parts, the polyreaction actuator temperature is increased to 60 ℃ by 40 ℃, by adding peroxide initiator initiated polymerization, and add activator to quicken initiation reaction; (B) above-mentioned polyreaction caused after 30～60 minutes, at monomer conversion is 50～70% o'clock, add aromatic ethenyl compound, 10～15 parts by weight of ethylene base prussiates, the emulsifying agent of 0.5～1.5 weight part and the emulsion of 20～30 parts by weight of deionized water that contains 10～15 weight parts in 2～3 hours continuously, the polyreaction actuator temperature progressively is increased to 70 ℃ by 60 ℃ lentamente; (C) when continuously adding emulsion, add peroxide initiator continuously in 2～3 hours; And (D) add above-mentioned emulsion (B) and above-mentioned peroxide initiator (C) after, once all add the activator and the peroxide initiators of acceleration initiation reactions, the polyreaction actuator temperature was increased to 80 ℃ by 70 ℃ in 1～2 hour, finish polymerization.
Based on the small grain size rubber latex of 100 weight parts, the content of described aromatic ethenyl compound can be 37.5～300 weight parts.When the content of aromatic ethenyl compound during less than 37.5 weight parts, welding strength is poor.When the content of aromatic ethenyl compound during greater than 300 weight parts, mobile and mechanical property reduction.
Based on the small grain size rubber latex of 100 weight parts, the content of described vinyl cyanide can be 25～250 weight parts.When the content of vinyl cyanide was not in above-mentioned scope, the chemical resistant properties of thermoplastic resin and shock strength reduced.
As everyone knows, described polymeric latex H 2SO 4, MgSO 4, CaCl 2Or Al 2(SO 4) 3Solidify, and washing, dehydration and drying are to obtain powdery polymer.
Described aromatic ethenyl compound can be selected from the group that comprises vinylbenzene, alpha-methyl styrene, α-ethyl styrene, p-vinyl toluene.Described vinyl cyanide is preferably selected from the group that comprises vinyl cyanide, methacrylonitrile and ethyl acrylonitrile.
The described emulsifying agent that is used in the polymerization is preferably alkylaryl sulfonate, alkali methyl alkyl vitriol, sulfonated alkyl ester, fatty acid ester, as the alkali salt of the rosinate of potassium rosinate etc., the mixture that they can be independent or two or more uses.
Described polymerization starter can be inorganic peroxide such as Sodium Persulfate or Potassium Persulphate, or the like.
The described promoting agent that is used to quicken the initiation reaction of superoxide can be formaldehyde sodium, sulfoxylate, edathamil sodium, ferrous sulfate, glucose, pyrrolin sodium or S-WAT.
Described molecular weight regulator is a mercaptan series, preferred tertiary lauryl mercaptan (tertiarydodecylmercaptan).
After finishing polymerization, the percentage of grafting of abs polymer can be 30% or higher.When percentage of grafting less than 30% the time, have the not naked rubber latex of grafted, so thermostability weakens.
α-Jia Jibenyixigongjuwu
Described α-Jia Jibenyixigongjuwu can be by copolymerization alpha-methyl styrene (AMS) monomer and the preparation of vinyl cyanide (AN) monomer.
Preferably, described α-Jia Jibenyixigongjuwu can be by preparing with alpha-methyl styrene (AMS) monomer of suitable ratio copolymerization 50～80 weight parts and vinyl cyanide (AN) monomer of 20～50 weight parts.
Based on 100 weight part alpha-methyl styrene (AMS) monomers, the content of acrylonitrile monemer can be 25～100 weight parts.When the content of acrylonitrile monemer was not in above-mentioned scope, the chemical resistant properties of thermoplastic resin and shock strength reduced.
Mass polymerization is preferably as polymerization process.Two-uncle as the molecular weight regulator-lauryl mercaptan that mixes monomer, 26～30 weight parts of 100 weight parts as the toluene and 0.1～1.0 weight part of solvent.In reactor, add this mixture continuously, and reacted 2～4 hours.At this moment, preferable reaction temperature remains on 140～170 ℃.
This preparation process is undertaken by the successive processes that comprises the pump, continuously stirring groove, fore-warmer tank and evaporator tank, the polymkeric substance that add raw material and carry pump and extrude processing unit (plant).
The multipolymer that imines replaces
Through continuous bulk polymerization or solution polymerization, prepare the multipolymer that described imines replaces by the method for preparing heat-resistant copolymer.That is, copolymerization aromatic ethenyl monomer and unsaturated dicarboxylic acid acid anhydride are to make styrene-maleic anhydride copolymer.Primary amine is added this styrene-maleic anhydride copolymer, carry out imines and replace, prepare the multipolymer that imines replaces thus.
When preparing the multipolymer of described imines replacement, behind the described styrene-maleic anhydride copolymer of preparation, use separator to remove unreacted aromatic ethenyl monomer, unsaturated dicarboxylic acid acid anhydride, solvent etc.This process allows to the addition polymerization of the aromatic ethenyl monomer of generation in imines replaces and the addition reaction of unsaturated dicarboxylic acid acid anhydride and primary amine minimizes.
(a) polymerization of aromatic ethenyl monomer and unsaturated dicarboxylic acid anhydride monomer
In this step, the mixture that will contain aromatic ethenyl monomer and initiator adds reactor respectively and carries out polymerization with the mixture that contains unsaturated dicarboxylic acid anhydride monomer and solvent.
Described aromatic ethenyl monomer can be styrene monomer, as vinylbenzene, alpha-methyl styrene, Vinyl toluene, t-butyl styrene or chlorostyrene or derivatives thereof.Preferably, use vinylbenzene.
Preferably, the raw material aromatic ethenyl monomer that contains 20～60wt% in the mixture of the mixture of aromatic ethenyl monomer and initiator and unsaturated dicarboxylic acid anhydride monomer and solvent.When the content of aromatic ethenyl monomer during, be difficult to obtain having enough stable on heating whole resins greater than 60wt%.
Described initiator can be organo-peroxide or azo-compound.The example of described organo-peroxide comprises ketone peroxide, ketal peroxide, super-oxide, dialkyl peroxide, the diaryl superoxide, peroxyester, peroxy dicarbonate, methylethyl ketone peroxide, the peroxidation methyl iso-butyl ketone (MIBK), the peroxidation methylcyclohexane, diacetone peroxide, 1,1-dibutyl mistake-3,3, the 5-trimethyl-cyclohexane, 1, the 1-dibutyl is crossed hexanaphthene, 2, the 2-dibutyl is crossed butane, 2,2,4-tri-methyl-amyl-2-hydrogen peroxide, dicumyl peroxide, 2,5-dimethyl-2,5-two-(tertiary butyl is crossed) hexane, the tert-butyl peroxide cumyl, di-t-butyl peroxide, three-(tertiary butyl is crossed) triazines, 1, two (tertiary butyl is crossed)-3 of 1-, 3,5-trimethyl-cyclohexane and di-t-butyl are crossed the hexahydro-terephthalate.
The example of described azo-compound comprises 1,1-azo two (hexanaphthene-1-nitrile), azo two-uncle-octane-2-cyano group-2-propyl group azoformamide, dimethyl-2,2-azo two (2 Methylpropionic acid ester) and 2,2-azo two (2-methylol propionitrile).The content of initiator can be 0.01～0.1wt% in the raw material.When the content of initiator during less than 0.01wt%, rate of polymerization reduces.When the content of initiator during, can not obtain the heat of desirable molecular weight and restive reactor greater than 0.1wt%.
The example of described unsaturated dicarboxylic acid anhydride monomer comprises maleic anhydride, imines acid anhydrides, citraconic anhydride and aconitic anhydride.Preferably, use maleic anhydride.
The content of unsaturated dicarboxylic acid anhydride monomer can be 10～30wt% in the raw material.When the content of unsaturated dicarboxylic acid anhydride monomer during, can not obtain desirable thermotolerance less than 10wt%.
The example of described solvent comprises ketone, dimethyl formamide and dimethyl sulfoxide (DMSO).Preferably, use methylethylketone (MEK), pimelinketone, methyl iso-butyl ketone (MIBK) (MIBK) or as the ketone of acetone.More preferably, use methylethylketone, pimelinketone or its mixture.
The content of solvent described in the raw material can be 20～60wt%.When the content of solvent during less than 20wt%, monomer is that the total amount of unsaturated dicarboxylic acid monomer+aromatic ethenyl compound is too high for the amount of solvent, therefore the viscosity of polymeric blends significantly improves in reaction process, and restive reaction heat, can cause problem in reaction process.When the content of solvent during greater than 60wt%, the amount of solvent is too high for monomeric total amount, the molecular weight of resin diminish and separator in the separation efficiency of solvent and unreacted monomer reduce.
Raw material is added a series of one or more reactors and carries out polymerization process.Even, preferably respectively it is added reactor because at room temperature aromatic ethenyl monomer and unsaturated dicarboxylic acid anhydride monomer also carry out polymerization.
Can adopt ordinary method to add respectively, but the mixture of the mixture of aromatic ethenyl monomer and initiator and unsaturated dicarboxylic acid anhydride monomer and solvent can prepare and add reactor respectively.
The example that can be used for reactor of the present invention comprise continuous stirred tank reactor (CSTR) (continuous stirred tank reactor, CSTR), plug flow reactor (plug flow reactor), staged reactor (multi-stage reactor).Preferably, use comprises continuous stirred tank reactor (CSTR).
Preferably 60～170 ℃, more preferably 80～150 ℃, most preferably 90～130 ℃ carry out polymerization.When polymerization temperature is lower than 60 ℃, can not get desirable rate of polymerization.When polymerization temperature is higher than 170 ℃, can not obtain desirable molecular weight.
In the rate of polymerization of unsaturated dicarboxylic acid anhydride monomer, the styrene-maleic anhydride copolymer of gained is preferably 90wt% in this step, more preferably 95wt% at least.
B) remove unreacted monomer
In this step, in the separator that polymkeric substance infeeds continuously with reactor is connected for preparing in the step a), to remove unreacted monomer and solvent.That is, polymeric solution in the step a) is infeeded separator continuously, to remove volatile constituent, as unreacted aromatic ethenyl monomer, unreacted unsaturated dicarboxylic acid anhydride monomer and solvent.
The example that can be used for separator of the present invention comprises flash evaporator, falls stream devolatilizer (falling strand devolatilizer), thin-film evaporator and vented extruder.Especially, preferably fall the stream devolatilizer and be applied to the present invention.
When separating unreacted monomer and solvent in falling the stream devolatilizer, the preferred temperature of drive condition is that 150～300 ℃ and pressure are 20～200 holders, and more preferably temperature is that 170～250 ℃ and pressure are 30～100 holders.
The unreacted monomer of removing in the separator and the content of solvent are preferably the 85wt% at least that adds its content before the separator, and more preferably at least 90%.
This step minimizes the addition polymerization of the aromatic ethenyl monomer that can take place in the imines substitution reaction and the addition reaction of unsaturated dicarboxylic acid acid anhydride and primary amine, so end product is free from foreign meter and thermotolerance improves.
C) imines substitution reaction
In this step, the mixture that will contain the active catalyst of the multipolymer melts of removing unreacted monomer and solvent, primary amine, imines substitution reaction infeeds the reactor that is connected with the separator of step b) continuously, to cause the imines substitution reaction.
The example of described primary amine comprises methylamine, ethamine, propylamine, butylamine, hexylamine, hexahydroaniline, decyl amine, aniline, Tolylamine, chloroaniline and bromaniline.Preferably, use aniline.
With respect to the amount of the unsaturated dicarboxylic acid acid anhydride in the multipolymer melts that adds in the separator, can use the primary amine of 0.5～2.0mol%.When the amount of primary amine during less than 0.5mol%, the thermostability of polymkeric substance and processibility reduce.When the amount of primary amine during, be difficult to remove the color change of unreacted primary amine residue and resin greater than 2.0mol%.
In the mixture of the active catalyst of primary amine, imines substitution reaction and solvent, the amount of primary amine is 10～40wt%.
The example of the active catalyst of primary amine substitution reaction comprises tertiary amine, as Trimethylamine, triethylamine and tributylamine.
The content of the active catalyst of described imines substitution reaction is the 10wt% of primary amine or littler.When the content of the active catalyst of imines substitution reaction during greater than 10wt%, the efficient of imines substitution reaction no longer improves.
Described solvent can with above-mentioned steps in a) used solvent phase with.The amount of solvent can be 0.5～1.5 times of amount of the resin (removing the multipolymer melts of unreacted monomer and solvent) of introducing the imines substitution reaction.When the amount of solvent during less than 0.5 times of the amount of the resin of introducing the imines substitution reaction, viscosity height, so the efficient of imines substitution reaction reduces, and is difficult to process.When the amount of solvent during greater than 1.5 times of the amount of the resin of introducing the imines substitution reaction, it causes burden for the evaporative process of next carrying out.
Will be by above-mentioned steps b) the separator active catalyst that contains multipolymer melts, primary amine, imines substitution reaction of discharging and the mixture of solvent uniform mixing and all the dissolving back add reactors.
Described imines substitution reaction is carried out in a series of one or more reactors.Described reactor can be continuous stirred tank reactor (CSTR) (CSTR), plug flow reactor or staged reactor.
Described imines substitution reaction preferably 100～250 ℃, more preferably 120～200 ℃, most preferably under 130～170 ℃, carry out.When temperature of reaction is lower than 100 ℃, can not obtain desired response speed.When temperature of reaction was higher than 250 ℃, primary amine may decompose.
The multipolymer based on maleinamide of gained is preferably at least 70mol%, more preferably 85mol%, 90mol% at least most preferably at least in the reaction product of primary amine.When the reaction product of primary amine during, based on the thermotolerance and the poor heat stability of the multipolymer of maleinamide less than 70mol%.
The multipolymer that the imines of gained replaces can have the aromatic ethylene base homopolymer (polystyrene) of 3wt% or littler content.When aromatic ethylene base homopolymer during greater than 3wt%, the thermotolerance of resin reduces and mechanical property weakens.
The multipolymer that imines prepared according to the methods of the invention replaces can have the thermotolerance that significantly improves, as 90% or the addition reaction of the high reaction efficiency of higher polymerisation conversion and the addition polymerization by making the aromatic ethenyl monomer that takes place in the imines substitution reaction and unsaturated dicarboxylic acid acid anhydride and primary amine minimize and in end product, do not have a homogeneous component of impurity.
Imine copolymer resin by method for preparing has 3wt% or littler aromatic ethylene base homopolymer (polystyrene) content and as the thermotolerance of the excellence of 170～190 ℃ second-order transition temperature (Tg).In addition, have as 90% or the high-level efficiency and excellent thermotolerance, weathering resistance and the mechanical property of the imines substitution reaction of higher polymerisation conversion based on the resin of imine copolymer.
Be used to improve the additive of prolongation property and shock strength
The described additive that is used to improve prolongation property and shock strength is the multipolymer of polymethylmethacrylate (PMMA) multipolymer, vinylbenzene and maleic anhydride or the multipolymer of α-Jia Jibenyixigongjuwu and maleic anhydride.
Described PMMA multipolymer can be selected from the group of the graft copolymer (PMMA-g-VA) of the graft copolymer (PMMA-g-EA) of graft copolymer (PMMA-g-MAH), methyl methacrylate and ethyl propenoate of the graft copolymer (PMMA-g-GMA), methyl methacrylate and the maleic anhydride that comprise methyl methacrylate and glycidyl methacrylate and methyl methacrylate and vinyl-acetic ester.The content of methyl methacrylate can be 20～80wt% in polymethylmethacrylate (PMMA) multipolymer.
In addition, cinnamic content can be 20～97wt% in the multipolymer of described vinylbenzene and maleic anhydride, and the content of α-Jia Jibenyixigongjuwu can be 20～97wt% in the multipolymer of described α-Jia Jibenyixigongjuwu and maleic anhydride.
The component of described additive and heat-proof ABS is that multipolymer and the α-Jia Jibenyixigongjuwu that imines replaces interacts to improve prolongation property and shock strength.
In addition, the thermoplastic resin composition of another embodiment comprises grafted ABS polymkeric substance, α-Jia Jibenyixigongjuwu and is used to improve wettable additive according to the present invention.This thermoplastic resin composition has performance-welding strength and wetting properties important in the excellent post-treatment step and keeps other physical propertiess.
What described thermoplastic resin composition can comprise the α-Jia Jibenyixigongjuwu of grafted ABS polymkeric substance, 20～80 weight parts of 20～40 weight parts and 0.1～5 weight part is used to improve wettable additive.
Based on the described grafted ABS polymkeric substance of 100 weight parts, the content of α-Jia Jibenyixigongjuwu can be 50～400 weight parts.When the content of α-Jia Jibenyixigongjuwu during less than 50 weight parts, shock strength, prolongation property or chemical resistant properties are poor.When the content of α-Jia Jibenyixigongjuwu during greater than 400 weight parts, tensile strength, thermotolerance, flowability and gloss difference.
Based on 100 weight part grafted ABS polymkeric substance, preferred described to be used to improve wettable content of additive be 0.25～25 weight part, 2.5～15 weight parts more preferably.When being used to improve wettable content of additive less than 0.25 weight part, wetting properties does not fully improve.When being used to improve wettable content of additive greater than 25 weight parts, thermotolerance and thermostability reduce.
Described grafted ABS polymkeric substance and α-Jia Jibenyixigongjuwu are as mentioned above.
Hereinafter, detailed description is used to improve wettable additive.
Be used to improve the surface of wettable additive based on ethylene glycol and modified resins, to improve in the post-treatment process, the particularly degree that coating extends on the heat-proof ABS surface in the spraying process behind the described thermoplastic resin composition of injection molding, i.e. wetting properties.As a result, the quantity that is used for obtaining at spraying process the spraying of desirable color can reduce, so post-treatment time and cost reduce.
By the chemical interaction between hydroxyl and the chemical solvents, hydroxyl attracts the reactive force of chemical solvents in the resin surface in the increase additive, can realize improving wettable effect by additive.
Describedly be used to improve wettable additive and can be and be selected from least a of the group that comprises polypropylene glycol, polyoxyethylene glycol or its segmented copolymer (polypropylene glycol/polyoxyethylene glycol).
Describedly be used to improve wettable additive and can have 500～5,000, preferred 1,000～4,000 weight-average molecular weight.When the weight-average molecular weight of additive less than 500 the time, can not play wettable effect that improves.When the weight-average molecular weight of additive greater than 5,000 o'clock, miscibility and mobile the reduction.
In embodiment of the present invention, the composition of described thermoplastic resin can comprise the multipolymer that imines replaces in addition and be used to improve the additive of prolongation property and shock strength.
Preferably, the composition of described thermoplastic resin can comprise multipolymer that the imines of α-Jia Jibenyixigongjuwu, 10～30 weight parts of grafted ABS polymkeric substance, 20～40 weight parts of 20～40 weight parts replaces, 1～10 weight part be used to improve the additive of prolongation property and shock strength and 0.1～5 weight part be used to improve wettable additive.
If necessary, described thermoplastic resin composition can comprise at least a additive that is selected from the group that comprises antioxidant, stablizer and lubricant in addition.
Described antioxidant prevents generable oxidation during mixing, extruding and the injection molding of preparation among the described thermoplastic resin composition.The example that can be used for antioxidant of the present invention comprises the primary antioxidants and the secondary antioxidants based on phosphorus that act as peroxide decomposer based on phenol that act as chain terminator.
Based on 100 weight part thermoplastic resin compositions, the content of antioxidant can be 0.1～5 weight part.When the content of described antioxidant during less than 0.1 weight part, the raising of thermostability is restricted.When the content of described antioxidant during greater than 5 weight parts, antioxidant decomposes, so thermostability significantly weakens, and only preparation cost improves.
Described lubricant makes the smooth surface of the end product that is prepared by described resin combination to improve processibility.In the present invention, can select to use lubricant for external use or with lubricator interior.With lubricator be present in described in the polymkeric substance,, therefore improve mobile to reduce the viscosity of resin itself.Described lubricant for external use has reduced the nip load between the polymer melt and metallic surface in the extrusion machine.Lubricant based on stearylamide can be used for the present invention.
Based on 100 weight part thermoplastic resin compositions, the content of described lubricant is 0.1～10 weight part, preferred 0.5～5 weight part.When the content of the lubricant of introducing during less than 0.1 weight part, the demoulding effect that is difficult in extrusion process in resin Composition model in dispersion rubber particle equably and the process of injection molding weakens, cause demoulding crack or hole albefaction (pin whitening), the value of product is reduced.When the content of lubricant during greater than 10 weight parts, can expect that the homogeneous of rubber grain disperses and the raising of mobile and shock resistance, but the thermotolerance reduction.
Described stablizer suppresses or prevents the thermolysis of plastics.The example that can be used for stablizer of the present invention comprises based on the material of phosphorus with based on the material of stearate.Based on the described thermoplastic resin composition of 100 weight parts, the content of described stablizer can be 0.1～5 weight part, preferred 0.1～2 weight part.When the content of described stablizer during, can not prevent thermolysis effectively less than 0.1 weight part.When the content of described stablizer during greater than 5 weight parts, this stablizer self decomposes, so thermostability significantly reduces.
The method for preparing thermoplastic resin composition of the present invention is not particularly limited and can uses ordinary method.Described thermoplastic resin composition can be by mixing described grafted ABS polymkeric substance, α-Jia Jibenyixigongjuwu and other additive preparation.Described thermoplastic resin composition can use the ordinary method extrusion molding, so that be extensive use of as the multiple parts of motor vehicle and electronics/electric product.
Hereinafter, by following examples the present invention is described in further detail.Yet scope of the present invention is not limited to following examples.
Be used for condition of molding of the present invention and the physical properties appreciation condition is as follows.
(1) extruding condition: LEISTRITZ MICRO 27 GL-36D, 240～260 ℃
(2) injection molding: ENGEL EC100 (80 TON), 240～260 ℃
(3) heat deflection temperature (HDT) (Heat deflection temperature, HDT): ASTM D-648
(4) chemical resistant properties (ESCR): the sample that injects is being remained on-20 ℃ chamber imposing on 1.3% strain, placing then 30 minutes.Using thinner (037u) after 20 minutes, observe the crack of generation.The following expression of observations: fine-A, good-B, general-C, poor-D, very poor-E.
(5) welding strength: the constant pressures of 20 crust are imposed on 350 ℃ hot plate 10 seconds, when separating the sample of injection, measure the length (cm) of the line of generation then by hot plate.
(6) prolongation property: ASTM D-638
(7) shock strength: ASTM D-256
(8) contact angle: in order to estimate wetting properties, resin placed room temperature following 24 hours or longer, measure this resin then and each is as the water of polar solvent with as the contact angle between the methylene iodide of non-polar solvent.Usually, when resin surface had the chemical solvents affinity, contact angle was low.
Preparation embodiment 1: preparation grafted ABS polymkeric substance
1) preparation small grain size rubber latex
With 100 parts by weight of deionized water, 100 weight parts as monomeric 1,3-butadiene, 1.2 weight parts as the potassium oleate of the potassium rosinate of emulsifying agent, 1.5 weight parts, 0.1 weight part as electrolytical yellow soda ash (Na 2CO 3), the KHCO of 0.5 weight part 3With the uncle-lauryl mercaptan as molecular weight regulator of 0.3 weight part (tert-dodecyl mercaptan, TDDM) once all introduce the polymerization reactor that nitrogen replaces (reactor, autoclave).Temperature of reaction is brought up to 55 ℃, passes through the Potassium Persulphate initiation reaction as initiator of disposable adding 0.3 weight part in reactor then, and reacts 10 hours.Thereafter, the season-lauryl mercaptan (TDDM) with 0.05 weight part adds reactant in addition, and temperature is brought up to 65 ℃ then, and reacts 8 hours, to make the small grain size rubber latex.
The gel content of the rubber latex of gained is 90%, exponent of expansion is 18, and particle diameter is
2) preparation volume particle size rubber latex (cohesive process of small grain size rubber latex)
The small grain size rubber latex of the above-mentioned preparation of 100 weight parts is added in the reactor, and stirring velocity is controlled at 10rpm, and temperature is controlled at 30 ℃, slowly adds the acetic acid aqueous solution of 3.0 weight parts 7% then in 1 hour in reactor., stop to stir, have large diameter conjugated diolefine latex in conjunction with the preparation of small grain size rubber latex by placing response thing 30 minutes thereafter.Adopt the volume particle size rubber latex of the methods analyst gained identical with the small grain size rubber latex.
The particle diameter of described volume particle size rubber latex is
Figure C20058000937900261
And its gel content is 90%, and its exponent of expansion is 17.
3) grafting step (preparation grafted ABS multipolymer):
Volume particle size rubber latex, the deionized water of 65 weight parts, 0.35 weight part of the above-mentioned preparation of 60 weight parts are once all introduced the polymerization reactor that nitrogen replaces as the ferrous sulfate of the potassium rosinate of emulsifying agent, the edathamil sodium of 0.1 weight part (sodium ethylene diaminetetraacetate), 0.005 weight part and the sodium sulfoxylate formaldehyde of 0.23 weight part, and temperature of reaction is brought up to 70 ℃.
The mixed emulsion that will contain the diisopropenyl hydrogen peroxide of the uncle-lauryl mercaptan of vinyl cyanide, 0.3 weight part of vinylbenzene, 8.2 weight parts of potassium rosinate, 19.2 weight parts of deionized water, 0.5 weight part of 40 weight parts and 0.3 weight part joined in the reactor in 2 hours continuously.Thereafter, the mixed emulsion that will contain the rare basic hydrogen peroxide of diisopropyl of the uncle-lauryl mercaptan of vinyl cyanide, 0.1 weight part of vinylbenzene, 3.0 weight parts of potassium rosinate, 9.6 weight parts of deionized water, 0.1 weight part of 10 weight parts and 0.1 weight part joined in the reactant in 1 hour continuously, and temperature is brought up to 80 ℃, and this reaction was finished in slaking in 1 hour then.
Wherein, the copolymerization transformation efficiency is 97.5%, and the solid type cured portion is 0.2%, and percentage of grafting is 37%.
This latex solidifies with aqueous sulfuric acid, and washing, makes powder thereafter.
Preparation embodiment 2: preparation α-Jia Jibenyixigongjuwu
70 weight part alpha-methyl styrenes, 30 parts by weight of acrylonitrile, 30 weight parts are introduced reactor as the toluene and 0.15 weight part of solvent continuously as the two-uncle-lauryl mercaptan of molecular weight regulator, wherein the reaction times is made as 3 hours, and temperature of reaction remains on 148 ℃.The polymeric solution that heating is discharged from reactor in preheater, and in the evaporation reaction device, evaporate unreacted monomer, the temperature of polymkeric substance remains on 210 ℃ then.By extrusion machine with transferpump acrylonitritrile-styrene resin (SAN type multipolymer) be processed as particle form thereafter.
Preparation embodiment 3: the multipolymer that imines replaces
Comprising that reactor that 3 of the arranged in series grooves that are used for mixing raw material, 3 are used to introduce monomeric groove and 2 vertical cylinder reactors carries out the preparation of the multipolymer that imines replaces.
(first process)
With the vinylbenzene of 38.2wt%, 0.01wt% as 1 of multi-functional initiator, two (tertiary butyl is crossed)-3 of 1-, 3, the mixture of the α-Jia Jibenyixierjuwu of 5-trimethyl-cyclohexane and 0.2wt% is introduced first groove that is used for mixing raw material, and the maleic anhydride of 16.4wt%, the methylethylketone of 16.4wt% and the pimelinketone of 29.1wt% are introduced second groove that is used for mixing raw material.Raw material with constant flow rate from each groove of mixing raw material introduced first reactor and polymerization thereafter.Polymeric solution is introduced separator continuously, and polymerisation conversion is made as 70wt% or higher in separator.At this moment, the temperature of first reactor remains on 120 ℃.
(second process)
To introduce from the polymeric solution of first reactor and fall stream and take off in the vaporizer, and remove unreacted monomer and solvent under holding in the palm at 180 ℃ and 250.
(the 3rd process)
Then, to contain with first process in the mixture of mixed solvent of 5 times methylethylketone of 3/100 times the triethylamine of aniline, aniline amount of the used identical mole number of maleic anhydride and aniline amount and pimelinketone be introduced in the polymeric solution of discharging from separator in second reactor, and carry out the imines substitution reaction, to obtain copolymer resin.At this moment, the temperature of second reactor remains on 140 ℃.
Embodiment 1
The grafted ABS polymkeric substance that mixes the preparation in preparation embodiment 1 of 30 weight parts, the α-Jia Jibenyixigongjuwu of 70 weight parts preparation in preparation embodiment 2, the conduct of 5 weight parts is used to improve PMMA-g-GMA (polymethylmethacrylate-g-glycidyl methacrylate, the PMMA: GMA=30wt%: 70wt%) of the additive of prolongation property and shock strength, 1.0 the H-WAX 200P (polyethylene wax) as lubricant of weight part, 0.2 weight part as the phenylbenzene Permethyl 99A. based phosphates of stablizer and the two-tert-butyl phosphenylic acid salt as antioxidant of 0.2 weight part.Then, prepare particle by use Bitruder (twin screwextruder) down at 240 ℃.
Embodiment 2
The PMMA-g-MAH (polymethylmethacrylate-g-maleic anhydride, the PMMA: MAH=30wt%: 70wt%), prepare particle that are used to improve the additive of prolongation property and shock strength except the conduct of adopting 5 weight parts with the method identical with embodiment 1.
Embodiment 3
AMSAN-MAH (the alpha-methyl styrene vinyl cyanide-g-maleic anhydride that is used to improve the additive of prolongation property and shock strength except the conduct of passing through reaction and the preparation of extruding α-Jia Jibenyixigongjuwu and maleic anhydride of adopting 5 weight parts, AMSAN: MAH=90wt%: 10wt%), prepare particle with the method identical with embodiment 1.
Comparative Examples 1
Mix multipolymer that the imines of α-Jia Jibenyixigongjuwu, the preparation in preparation embodiment 3 of 30 weight parts of grafted ABS polymkeric substance, the 40 weight parts preparation in preparation embodiment 2 of 30 weight parts preparation in preparation embodiment 1 replaces, 1.0 weight parts the H-WAX 200P (polyethylene wax) as lubricant, 0.2 weight part as the phenylbenzene Permethyl 99A. based phosphates of stablizer and the two-tert-butyl phosphenylic acid salt as antioxidant of 0.2 weight part.Then, under 240 ℃, prepare particle by the use Bitruder.
Comparative Examples 2
Mix multipolymer that the imines of α-Jia Jibenyixigongjuwu, the preparation in preparation embodiment 3 of 30 weight parts of abs polymer that 30 weight parts provide by LG Chemical Ltd., the preparation in preparation embodiment 2 of 40 weight parts replaces, 1.0 weight parts the H-WAX200P as lubricant (polyethylene wax), 0.2 weight part as the phenylbenzene Permethyl 99A. based phosphates of stablizer and the two-tert-butyl phosphenylic acid salt as antioxidant of 0.2 weight part.Then, under 240 ℃, prepare particle by the use Bitruder.
Comparative Examples 3
Mix the α-Jia Jibenyixigongjuwu, 30 weight parts of grafted ABS polymkeric substance, the 40 weight parts preparation in preparation embodiment 2 of 30 weight parts preparation in preparation embodiment 1 N-phenylmaleimide (DENKA-IP (MS-NB) as heat-resisting toughener, DENKA, Japan), the H-WAX 200P (polyethylene wax) as lubricant of 1.0 weight parts, 0.2 weight part as the phenylbenzene Permethyl 99A. based phosphates of stablizer and the two-tert-butyl phosphenylic acid salt as antioxidant of 0.2 weight part.Then, under 240 ℃, prepare particle by the use Bitruder.
Under 240 ℃, inject the particle of preparation in embodiment 1～3 and the Comparative Examples 1～3 once more, and measure heat deflection temperature (HDT), welding strength, prolongation, shock strength and chemical resistant properties.The results are shown in table 1.
Table 1
Embodiment 1 Embodiment 2 Embodiment 3 Comparative Examples 1 Comparative Examples 2 Comparative Examples 3
Heat deflection temperature (HDT) (℃, 1/4 ") 115.5 115.8 115.9 115.4 115.3 115.9
Welding strength (cm) 0.0 0.0 0.0 0.0 7.0 0.0
Prolongation property (%) 25 22 15 13 20 10
Shock strength (J/m, 1/8 ") 110 108 100 98 98 90
Chemical resistant properties (ESCR) A A B B D D
As seen in Table 1, according to the thermoplastic resin composition of embodiments of the invention 1～3 than Comparative Examples 1～3 in excellence aspect shock strength, welding strength and the chemical resistant properties.
Embodiment 4
The weight-average molecular weight that the conduct that mixes α-Jia Jibenyixigongjuwu, 1 weight part of grafted ABS polymkeric substance, the 40 weight parts preparation in preparation embodiment 2 of 30 weight parts preparation in preparation embodiment 1 improves wettable additive be 2,000 glycol polypropylene, 1.0 weight parts the H-WAX 200P (polyethylene wax) as lubricant, 0.2 weight part as the phenylbenzene Permethyl 99A. based phosphates of stablizer and the two-tert-butyl phosphenylic acid salt as antioxidant of 0.2 weight part.Then, under 240 ℃, prepare particle by the use Bitruder.
Embodiment 5
Except comprising that in addition as being used to improve wettable additive, weight-average molecular weight be outside 3,500 the glycol polypropylene, prepare particle with the method identical with embodiment 4.
Comparative Examples 4
Except comprising that in addition as being used to improve wettable additive, weight-average molecular weight be 425 the glycol polypropylene, prepare particle with the method identical with embodiment 4.
Under 240 ℃, inject the particle of preparation in embodiment 4～5 and the Comparative Examples 4 once more, and measure heat deflection temperature (HDT), welding strength, prolongation, shock strength, chemical resistant properties and contact angle.The results are shown in table 2.
Table 2
Embodiment 4 Embodiment 5 Comparative Examples 1 Comparative Examples 4
Heat deflection temperature (HDT) (℃, 1/4 ") 115.5 115.8 115.4 115.0
Welding strength (cm) 0.0 0.0 0.0 0.1
Prolongation property (%) 25 25 13 25
Shock strength (J/m, 1/8 ") 110 106 98 109
Chemical resistant properties (ESCR) A A B A
Contact angle (°) (methylene iodide) 9.4 8.2 29.7 30.0
As seen in Table 2, compare with 4 with Comparative Examples 1, according to being used to improve the embodiment 4 of wettable additive and 5 thermoplastic resin composition has improved shock strength, welding strength of the present invention comprising, and chemical resistant properties and the contact angle that reduces.

Claims (8)

1, a kind of thermoplastic resin composition comprises multipolymer that grafted ABS polymkeric substance, α-Jia Jibenyixigongjuwu, imines replace and the additive that is used to improve prolongation property and shock strength,
Wherein, described grafted ABS polymkeric substance is by copolymerization
The median size of 10～40 weight parts is 800～1,500
Figure C2005800093790002C1
And gel content is 80～90% content of polybutadiene rubber latex;
The median size of 15～30 weight parts is 2,500～3,500 And gel content is 80～90% content of polybutadiene rubber latex;
The aromatic ethenyl compound of 15～30 weight parts; And
The vinyl cyanide compound of 10～25 weight parts and preparing,
Wherein, described α-Jia Jibenyixigongjuwu prepares by copolymerization alpha-methyl styrene and vinyl cyanide,
Wherein, the described additive that is used to improve prolongation property and shock strength is the multipolymer of polymethyl methacrylate copolymer, vinylbenzene and maleic anhydride or the multipolymer of α-Jia Jibenyixigongjuwu and maleic anhydride,
Wherein, described polymethyl methacrylate copolymer is selected from the group of the graft copolymer of the graft copolymer of graft copolymer, methyl methacrylate and ethyl propenoate of the graft copolymer, methyl methacrylate and the maleic anhydride that comprise methyl methacrylate and glycidyl methacrylate and methyl methacrylate and vinyl-acetic ester
Wherein, the multipolymer that described imines replaces is to form multipolymer by copolymerization aromatic ethenyl monomer and unsaturated dicarboxylic acid anhydride monomer, and primary amine added prepares in this multipolymer.
2, thermoplastic resin composition according to claim 1 comprises the multipolymer that the imines of α-Jia Jibenyixigongjuwu, 10～30 weight parts of grafted ABS polymkeric substance, 20～80 weight parts of 20～40 weight parts replaces and the additive that is used to improve prolongation property and shock strength of 1～10 weight part.
3, thermoplastic resin composition according to claim 1 comprises the multipolymer that the imines of α-Jia Jibenyixigongjuwu, 10～30 weight parts of grafted ABS polymkeric substance, 20～40 weight parts of 20～40 weight parts replaces and the additive that is used to improve prolongation property and shock strength of 1～10 weight part.
4, thermoplastic resin composition according to claim 1, wherein, described aromatic ethenyl compound is selected from the group that comprises vinylbenzene and alpha-methyl styrene.
5, thermoplastic resin composition according to claim 1, wherein, described vinyl cyanide compound is selected from the group that comprises vinyl cyanide, methacrylonitrile and ethyl acrylonitrile.
6, thermoplastic resin composition according to claim 1, wherein, described α-Jia Jibenyixigongjuwu is by the vinyl cyanide preparation of the alpha-methyl styrene and 20～50 weight parts of copolymerization 50～80 weight parts.
7, thermoplastic resin composition according to claim 1 also comprises at least a additive that is selected from the group that comprises antioxidant, stablizer and lubricant.
8, thermoplastic resin composition according to claim 7, wherein, based on the described thermoplastic resin composition of 100 weight parts, the content of antioxidant is 0.1～5 weight part, the content of stablizer is 0.1～5 weight part, and the content of lubricant is 0.1～10 weight part.
CNB2005800093791A 2004-12-31 2005-12-30 Have improved thermotolerance, welding strength, chemical resistant properties, shock strength, prolongation and wettable Plastic Resin composition Active CN100549088C (en)

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