CN1322221A - Body add-on parts based on thermoplastic polyketones - Google Patents

Body add-on parts based on thermoplastic polyketones Download PDF

Info

Publication number
CN1322221A
CN1322221A CN99811855A CN99811855A CN1322221A CN 1322221 A CN1322221 A CN 1322221A CN 99811855 A CN99811855 A CN 99811855A CN 99811855 A CN99811855 A CN 99811855A CN 1322221 A CN1322221 A CN 1322221A
Authority
CN
China
Prior art keywords
polyketone
japanning
mixture
acid
preferred
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Pending
Application number
CN99811855A
Other languages
Chinese (zh)
Inventor
M·米勒
D·约阿西米
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Bayer AG
Original Assignee
Bayer AG
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Bayer AG filed Critical Bayer AG
Publication of CN1322221A publication Critical patent/CN1322221A/en
Pending legal-status Critical Current

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G67/00—Macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing oxygen or oxygen and carbon, not provided for in groups C08G2/00 - C08G65/00
    • C08G67/02—Copolymers of carbon monoxide and aliphatic unsaturated compounds
    • C—CHEMISTRY; METALLURGY
    • 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
    • C—CHEMISTRY; METALLURGY
    • 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
    • C08L25/12—Copolymers of styrene with unsaturated nitriles
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • 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
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L73/00—Compositions of macromolecular compounds obtained by reactions forming a linkage containing oxygen or oxygen and carbon in the main chain, not provided for in groups C08L59/00 - C08L71/00; Compositions of derivatives of such polymers

Landscapes

  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Compositions Of Macromolecular Compounds (AREA)
  • Vehicle Interior And Exterior Ornaments, Soundproofing, And Insulation (AREA)

Abstract

The invention relates to body add-on parts based on thermoplastic polyketones and blends thereof with other polymers. The invention also relates to the use of thermoplastic polyketones for producing body add-on parts.

Description

Car body accessory based on the thermoplasticity polyketone
The present invention relates to based on the thermoplasticity polyketone and with the car body accessory of other mixture of polymers and thermoplasticity polyketone to producing the application of car body accessory.
Because design and cost, plastics are still increasing in the use of car body outside.Therefore, the importance of the plastic fittings of the painted japanning of vehicle is increasing.The design flexibility of plastic automotive accessory is more much bigger than using metal.Particularly in the big car body outside of surface-area, use plastic fittings that huge cost advantage can be provided, the production lot of vehicle just can be more little, and the cost advantage loss is big more.
The japanning of plastic automotive accessory is that off-line carries out basically, both can also can carry out in the plastics japanning workshop of automobile factory in supplier's factory building.Under the situation of comprehensive japanning, the initial japanning line of the accessory of off-line japanning terminal is installed on the car body.The advantage of off-line japanning is, can adopt special japanning equipment, and the performance of these japanning equipment is particularly suitable for plastic material and application purpose.In the thermoplastic material scope, select plastics to be actually unrestricted.Yet the shortcoming of off-line japanning is that deviation might take place in color harmony gloss aspect, upward price height, investment and production cost height, service and the logistical costs of paint material are also more expensive.
In order to overcome the shortcoming of off-line japanning, in car body japanning process, can send into plastic fittings and can be partially or completely in vehicle body japanning process applied plastic accessory simultaneously.The integrated online insertion or the online japanning of being called of this plastic fittings in car body japanning process.
Under the situation of inserting online japanning,, plastic fittings is sent in the initial japanning production line behind the priming (for example adopting negative electrode to immerse japanning) and before or after applying filler.For being inserted in line method, plastic fittings also must be able to adopt electrostatic coating method japanning.This priming paint that will adopt conductive plastics or for example adopt off-line to be coated with conduction reaches.At the baking filler with when going up subsequently enamelled coating (generally the first layer be priming paint, be varnish then), the plastics of plastic fittings must be under up to 160 ℃ temperature ability regular hour (for example 30 minutes) and not damaging.The shortcoming that is inserted in line method is to need the separate cleaning plastic fittings.In addition, behind priming, on the japanning production line, send into the danger that plastic fittings includes pollution.
Online japanning means and before the car body priming plastic fittings is installed on the car body that then, these plastic fittingss are by whole original japanning processes.Therefore, under the situation of online japanning, plastic fittings is through and through by the japanning line.When adopting online japanning, whole vehicle body on mounting rack and mounted accessory, or with accessory on the device anchor clamps together for example, at first in steeping vat, remove degrease, carry out phosphatizing and priming (generally being to adopt the negative electrode dip-coating), toast priming paint down up to 230 ℃ in temperature.Again be inserted in the further japanning of mode identical described in the line method.Owing to, between two japanning positions, do not send into plastic fittings, prevented the danger of polluting in line method.Off-line be inserted in line method and compare, directly be assemblied on the cost quite favourable.Online japanning need use the plastics to the temperature ability certain hour that (is generally 160-210 ℃) up to 230 ℃ (for example 30 minutes).Be fit to online use but nonconducting plastics, also need the priming paint of coating electrically conductive in advance sometimes.
In the car body japanning that auto parts machinery is integrated, advantage that adopt to insert online or online japanning method japanning is: reduce the japanning cost, simplify japanning method, better and the tone consistence of car body and consistence, the logistics of effect more simplify.
For inserting online and at line method, the requirement to high heat resistance and at low temperatures high tenacity combine has hindered the application of the effective thermoplastics of nearly all cost in vehicle body japanning integral method.The fortification substance that adds in thermoplastics (for example, glass fibre, talcum, kaolin and wollastonite) though improved thermotolerance and reduced thermal expansivity, causes loss in toughness at low temperatures.In thermoplastics, add impact-resistant properties-correcting agent (for example ABS-rubber, EPDM-rubber),, cause thermotolerance not enough though improved low-temperature flexibility.In the thermoplastics scope, have only polyphenylether/polyamide mixture (PPO/PA) to have required thermotolerance, have commercial value.The PPO/PA mixture is mainly used at present by inserting online or at the splash pan of line method japanning.Yet the shortcoming of PPO/PA mixture is that low-temperature flexibility is relatively poor and water regain is big.Water absorbing capacity causes the variation of size, and influential to the performance of japanning.Another shortcoming is that the PPO/PA mixture is made up of the thermoplastics of unbodied thermoplastics and partial crystallization, their very difficult mixing.Can to reproduce phase morphology and, need to adopt compatilizer in order to produce for fear of separation phenomenon.Except increasing cost, the PPO/PA under working condition occurs some problems to guaranteeing aspect the consistent quality product in complicacy chemical and physically.
Have now found that, the thermoplasticity polyketone and with the mixture of other thermoplastics, but have the desirable properties that the auto parts machinery of online or online japanning is inserted in a series of suitable employings.Polyketone is the thermoplastics of partial crystallization, but under the high temperature that inserts online or online japanning method employing, has enough rigidity, thermotolerance and dimensional stability.Polyketone and with the mixture of other thermoplastics, it is characterized in that having good shock-resistance at low temperatures, and from environment, absorb any moisture hardly.Their hydrolysis, and very well fuel resistance is arranged, and can form effective sealing coat to fuel.They have extraordinary recovery characteristic.Do not adopt halogen or phosphorus, just polyketone can be made nonflammable.In addition, they are based on cheap raw material, for example carbon monoxide, ethene and propylene.
Particularly, polyketone and have high temperature resistant and impact-resistant at low temperatures excellent comprehensive performance with the mixture of other thermoplastics.In addition, they can adopt conventional plastic processing technology, and for example the combination of injection molding, extruding, thermoforming and deep-draw, compacting, welding, die and these technology is processed.
The invention provides auto parts machinery and car body accessory based on the thermoplasticity polyketone.
Based on the thermoplasticity polyketone and also can based on the auto parts machinery of the mixture of other thermoplastics, be fit to very much insert online and online japanning.These auto parts machineries are particluarly suitable for the line japanning.
The thermoplasticity polyketone can mix with other thermoplastics as mixing element, thermoplastic elastomer or its mixture.These thermoplastic compositions that comprise thermoplasticity polyketone and other mixing element also are particularly suitable for auto parts machinery.
The present invention also provide use heat plasticity polyketone and with the application in producing auto parts machinery and car body accessory of the mixture of other thermoplastics, thermoplastic elastomer and their mixture.
The thermoplasticity polyketone has the straight chain cross structure, and the unsaturated hydrocarbons of each molecule comprises the carbon monoxide of 1 molecule on substantially.Suitable alkene layer unsaturated hydrocarbon monomer as the polyketone synthesis polymkeric substance, its carbon atom is up to 20, preferably up to 10, they are aliphatic monomer such as ethene and other alkene such as propylene, 1-butylene, 1-iso-butylene, 1-hexene, 1-octene and 1-dodecylene, or the aromatic yl aliphat monomer, on a carbon atom of straight chain, comprise an aryl substituent.As the monomeric example of aromatic yl aliphat, can be listed below: vinylbenzene, alpha-methyl styrene, right-ethyl styrene and-isopropyl benzene ethene.
Preferred polyketone is the multipolymer of carbon monoxide and ethene, or carbon monoxide, ethene and have second kind of ethylenically unsaturated hydrocarbons, particularly alpha-olefin of at least 3 carbon atoms, for example the trimer of propylene.
The special preferably trimer of at least 2 kinds of monomeric units, one of them is an ethene, another kind is second kind of hydrocarbon.The preferred second kind of hydrocarbon that adopts about 10-100 monomeric unit.
The polymer chain of preferred polyketone can be represented by the formula:
[CO(CH 2CH 2)] x[CO(G)] y????????????????(I)
In the formula
G is based on a kind of at least 3 carbon atoms that have, the monomeric unit of the ethylenically unsaturated hydrocarbons of preferred 3-10 carbon atom, they be by the olefinic double bond polymeric and
Ratio y: x is not more than about 0.5.
For the multipolymer of carbon monoxide and ethene, y=0.
If y is not equal to 0, then adopt trimer, unit-CO-(CH 2CH 2)-and-CO-(G)-have statistical distribution along polymer chain.
The value of preferred proportion y: x is 0.01-0.1.
According to gel permeation chromatography, the molecular-weight average (number-average molecular weight) of preferred polyketone is about 1,000-200, and 000, be preferably 20 especially, 000-90,000.
Further data about polyketone characteristic and preparation can be with reference to United States Patent (USP)-A 5 166252.
Can adopt the mixture of polyketone or polyketone.
Example as mixing element is listed below: polyalkylene terephthalate, thermoplastic vinyl (being total to) polymkeric substance, graftomer (for example ABS-rubber, acrylate-rubber), polyolefine and thermoplastic elastomer such as thermoplastic polyurethane, EP (D) M-rubber, polypropylene (PP)/EPDM-rubber, polyphenylene oxide and composition thereof.
Under situation of the present invention, the polyalkylene terephthalate is aromatic binary carboxylic acid or its reactive derivatives (for example dimethyl esters or acid anhydrides) and aliphatics, alicyclic or the reaction product of aromatic yl aliphat dibasic alcohol and the mixture of these reaction product.
Preferred polyalkylene terephthalate, be by terephthalic acid (or its reactive derivatives) and have the aliphatics of 2-10 carbon atom or alicyclic dibasic alcohol by known method (Kunststoff-Handbuch (plastics handbook), vol.VIII, p.695 etseq., Karl-Hansar press, Munich, 1973) preparation.
Preferred polyalkylene terephthalate, di-carboxylic acid comprises at least 80%, the terephthalic acid group of preferred 90% (mole) relatively, comprise at least 80% with relative glycol component, the ethylene glycol of preferred 90% (mole), and/or 1, ammediol group, and/or 1,4 butyleneglycol group.
Except the terephthalic acid group, preferred polyalkylene terephthalate can comprise other aromatic dicarboxylate's group with 8-14 carbon atom up to 20% (mole), or has an aliphatic dicarboxylic acid group of 4-12 carbon atom, for example phthalic acid, iso-phthalic acid, naphthalene-2,6-di-carboxylic acid, 4, the group of 4 '-phenylbenzene di-carboxylic acid, Succinic Acid, hexanodioic acid, sebacic acid, nonane diacid, cyclohexanediacetic.
Except ethylene glycol, or 1, ammediol, or 1, beyond the 4-butyleneglycol group, preferred polyalkylene terephthalate can comprise other aliphatic dihydroxy alcohol with 3-12 carbon atom up to 20% (mole), or have a cycloaliphatic diols of 6-21 carbon atom, and for example 1, ammediol, 2-ethyl-1, ammediol, neopentyl glycol, 1, the 5-pentanediol, 1, the 6-hexylene glycol, hexanaphthene-1, the 4-dimethanol, 3-methyl-2, the 4-pentanediol, 2-methyl-2, the 4-pentanediol, 2,2,4-trimethylammonium-1, the 3-pentanediol, 2,2,4-trimethylammonium-1, the 5-pentanediol, 2-ethyl-1, the 3-hexylene glycol, 2,2-diethyl-1, ammediol, 2, the 5-hexylene glycol, 1,4-two-(beta-hydroxy oxyethyl group)-benzene, 2,2-pair-(4-hydroxy-cyclohexyl)-propane, 2,4-dihydroxyl-1,1,3,3-tetramethyl-ring butane, 2,2-pair-(3-beta-hydroxy ethoxyl phenenyl)-propane and 2,2-pair-(4-hydroxyl propoxy-phenyl)-(German Patent-OS 24 07 674 for propane, 24 07 776 and 27 15 932).
Can by for example described in German Patent-OS 19 00 270 and the United States Patent (USP)-PS 3 692 744 like that, by adding the ternary or the tetravalent alcohol of relatively small amount, or ternary or quaternary carboxylic acid, make polyalkylene terephthalate collateralization.The example of preferred branching agent is trimesic acid, trihemellitic acid, methyltrimethylolmethane, trihydroxymethyl propane and tetramethylolmethane.
With respect to sour composition, adopt the branching agent that is no more than 1% (mole) to suit.
Preferred especially only by terephthalic acid and reactive derivatives (for example its dialkyl) and ethylene glycol and/or 1, ammediol and/or 1, the mixture of the polyalkylene terephthalate of 4-butyleneglycol preparation (poly-ethylidene terephthalate and polybutylene terephthalate) and these polyalkylene terephthalates.
Preferred polyalkylene terephthalate also is the copolyesters by at least two kinds of above-mentioned sour compositions and/or at least two kinds of above-mentioned pure composition preparations.Particularly preferred copolyesters is poly-(ethylene glycol/1,4-butyleneglycol) terephthalate.
Adopt phenol/neighbour-dichlorobenzene (w/w is 1: 1) to measure down at 25 ℃, the limiting viscosity of polyalkylene terephthalate is generally about 0.4-1.5, preferred 0.5-1.3.
Under situation of the present invention, thermoplastic urethane is by the straight chain polyvalent alcohol, generally is polyester polyol or polyether glycol, organic diisocyanate and short chain dibasic alcohol (chain extension agent) preparation.The catalyzer that can add quickens preparation feedback.The mol ratio of constituent can change in very wide scope, this means the character that can regulate product.Verified, the molar ratio of polyvalent alcohol and chain extension agent is 1: 1-1: the 12nd, effectively.The product of this method preparation, hardness is Shore (Shore) A level 70 to D levels 75.But the polyurethane elastomer of thermoplasticity processing can be by the method for fractional steps (prepolymer method), or by the method (Completion Techniques) of the reaction preparation simultaneously in a step of all compositions.In the prepolymer method, prepare a kind of prepolymer that comprises isocyanic ester by polyvalent alcohol and vulcabond, this polymkeric substance reacts with chain extension agent in second step.Can prepare TPU in mode continuous or that be interrupted.The most familiar preparation method is belt method and extrusion machine method.
Thermoplastic urethane can be made by the composition reaction of following production urethane:
A) organic diisocyanate,
B) molecular weight is the straight chain terminal hydroxy group polyvalent alcohol of 500-5000,
C) molecular weight is dibasic alcohol or the diamine chain extension agent of 60-500,
Wherein at A) in the NCO group, and at B) and C) in be that the molar ratio of reactive group is 0.9-1.2 to isocyanic ester.
Suitable organic diisocyanate A) be, for example at Justus Liebigs Annalender Chemie, 562, the p.75-136 aliphatics described in, alicyclic, aromatic yl aliphat, heterocycle and aromatic diisocyanate.
As an example, itemizing is as follows: aliphatic diisocyanate, for example hexamethylene diisocyanate; Alicyclic diisocyanate, isophorone diisocyanate, 1 for example, 4-cyclohexyl diisocyanate, 1-methyl-2,4-cyclohexyl diisocyanate, 1-methyl-2,6-cyclohexyl diisocyanate and corresponding isomer mixture, 4,4 '-dicyclohexyl methane diisocyanate, 2,4 '-dicyclohexyl methane diisocyanate and 2,2 '-dicyclohexyl methane diisocyanate and corresponding isomer mixture; Aromatic diisocyanate, for example 2, the 4-tolylene diisocyanate, 2,4-tolylene diisocyanate and 2, the mixture of 6-tolylene diisocyanate, 4,4 '-diphenylmethanediisocyanate, 2,4 '-diphenylmethanediisocyanate and 2,2 '-diphenylmethanediisocyanate, 2,4 '-diphenylmethanediisocyanate and 4,4 '-mixture of diphenylmethanediisocyanate, the liquid state 4 of urethane modification, 4 '-diphenylmethanediisocyanate and 2,4 '-diphenylmethanediisocyanate, 4,4 '-two isocyano network phenylbenzene-ethane (1,2) and 1,5-naphthalene diisocyanate.Preferred employing 1,4 of hexamethylene-diisocyanate, isophorone diisocyanate, dicyclohexyl methane diisocyanate, diphenylmethanediisocyanate and content＞96% (weight), 4 '-isomer mixture of diphenylmethanediisocyanate, preferred especially 4,4 '-diphenylmethanediisocyanate and 1, the 5-naphthalene diisocyanate.Can use described vulcabond individually or with the form of its mixture.Also can with they with up to the polymeric polyisocyanate of 15% (weight) (according to the vulcabond total), for example triphenyl methane 4,4 ', 4 " triisocyanate or polyphenylene-polymethylene-polymeric polyisocyanate uses together.
The polyvalent alcohol of the straight chain terminal hydroxy group of employing molecular weight 500-5000 is as composition B).They often comprise a spot of non-straight chain compound, decide on the preparation method.Therefore, these compounds often are also referred to as " polyvalent alcohol that is straight chain basically ".Preferred polyester diol, polyether Glycols, polycarbonate diol or their mixture of adopting.
Suitable polyether Glycols is the raw molecule prepared in reaction that makes one or more desaturation oxygen that have 2-4 carbon atom on alkylidene group and comprise the active hydrogen atom of two bondings.Can list following compounds as oxirane, for example: oxyethane, 1,2 epoxy prapane, epichlorohydrin, 1,2-butylene oxide ring and 2,3-butylene oxide ring.The preferred mixture that adopts oxyethane, propylene oxide and 1,2 epoxy prapane and oxyethane.Oxirane can be individually, use alternately with each other or with the form of mixture.The compound that is suitable as the raw molecule use is as follows: water; Amino alcohol such as N-alkyl diethanolamine, for example N methyldiethanol amine; With dibasic alcohol such as ethylene glycol, 1, ammediol, 1,4-butyleneglycol and 1,6-hexylene glycol.Also can use the raw molecule mixture.The tetrahydrofuran by polymerization product of hydroxyl also is the polyether Glycols that suits.Though also can use the three function polyethers of counting 0-30% (weight) by two function polyethers, but usage quantity is to want to prepare the thermoplasticity product processed at the most.Basically the molecular weight that is the polyether Glycols of straight chain is 500-5000.They can use individually, and form that also can its mixture is used.
Suitable polyester diol for example can be by 2-12 carbon atom, the dicarboxylic acid of preferred 4-6 carbon atom and polyvalent alcohol preparation.Suitable dicarboxylic acid for example is: aliphatic dicarboxylic acid such as Succinic Acid, pentanedioic acid, hexanodioic acid, suberic acid, nonane diacid, sebacic acid; With aromatic dicarboxylic acid such as phthalic acid, iso-phthalic acid and terephthalic acid.Dicarboxylic acid can use separately, also can use with form of mixtures, for example uses with the form of Succinic Acid, pentanedioic acid and hexanodioic acid mixture.In order to prepare polyester diol, also can adopt the derivative of corresponding dicarboxylic acid, it is favourable that carboxylic acid diesters, carboxylic acid anhydride or the chlorinated carboxylic acid that for example has 1-4 carbon atom on alcohol radical replaces di-carboxylic acid.Examples of polyhydric alcohols is to have 2-10, the dibasic alcohol of preferred 2-6 carbon atom, for example ethylene glycol, Diethylene Glycol, 1,4-butyleneglycol, 1,5-pentanediol, 1,6-hexylene glycol, decamethylene-glycol, 2,2-dimethyl-1, ammediol, 1, ammediol and dipropylene glycol.According to required character, can also can use polyvalent alcohol individually with the form of its mixture.The ester class of carbonic acid and above-mentioned dibasic alcohol, particularly with dibasic alcohol with 4-6 carbon atom, for example 1,4-butyleneglycol or 1, the ester class of 6-hexylene glycol; The condensation product of hydroxycarboxylic acid, for example condensation product of hydroxycaproic acid; With the polymerisate of lactone, for example, the polycaprolactone of replacement also suits.The preferred following compounds that adopts is as polyester diol: ethylene glycol-polyester adipate, 1,4-butyleneglycol-polyester adipate, ethylene glycol-1,4-butyleneglycol-polyester adipate, 1,6-hexylene glycol-neopentyl glycol-polyester adipate, 1,6-hexylene glycol-1,4-butyleneglycol-polyester adipate and polycaprolactam.The molecular weight of polyester diol is 500-5000, and polyester diol can be used separately, and form that also can its mixture is used.
Adopting molecular weight is that the dibasic alcohol of 60-500 or diamine are as chain extension agent C), the aliphatic dihydroxy alcohol of preferred 2-14 carbon atom, ethylene glycol, 1 for example, 6-hexylene glycol, Diethylene Glycol, dipropylene glycol, preferred especially 1,4-butyleneglycol.Yet terephthalic acid also suits with the dibasic ester class of the ethylene glycol generation that 2-4 carbon atom arranged, for example, and terephthalic acid-two-ethylene glycol, or terephthalic acid-two-1,4-butyleneglycol; The inferior hydrocarbyl ether of the hydroxyl of quinhydrones, for example 1,4-two-(hydroxyethyl)-quinhydrones; The bis-phenol of ethoxylation; (ring) aliphatic diamine, for example isophorone diamine, 1,1,2-propylene diamine, 1,3-propylene diamine, N-methyl propylidene-1,3-diamines, N, N '-dimethyl ethylene diamine; And aromatic diamine, for example 2,4-toluylene diamine and 2,6-toluylene diamine, 3,5-diethyl-2,4-toluylene diamine and 3,5-diethyl-2,6-toluylene diamine; Be mainly one, two, three or quaternary 4,4 '-diaminodiphenyl-methane.Also can adopt above-mentioned chain extension agent mixture.In addition, also can use more a spot of trivalent alcohol.
And, also can use conventional single functional compounds slightly, for example as chain termination agent or releasing agent.Can be listed below as an example: alcohols such as octanol and stearyl alcohol; Or amine such as butylamine and stearylamide.
In order to prepare thermoplastic urethane, also can be in the presence of catalyzer, auxiliary substance and additive, constituent is reacted, the consumption of constituent is, NCO group and NCO-reactive group total amount, particularly the ratio of the OH group total amount in low molecular weight diol/trivalent alcohol and the polyvalent alcohol is 0.9: 1.0-1.2: 1.0, preferred 0.95: 1.0-1.10: 1.0.
Suitable catalyzer is that prior art is known, comprising the tertiary amine of routine, and for example triethylamine, dimethylcyclohexylamine, N-methylmorpholine, N, N '-lupetazin, 2-(dimethylamino oxyethyl group)-ethanol, heavy azabicyclic-(2,2,2)-octane etc.; And particularly metallic compound, for example titanic acid ester, iron cpd, tin compound, for example dialkyltin salts such as dibutyltin diacetate, the dibutyl tin laurate etc. of oxalic acid tin, two stannous octoates, two lauric acid tin or aliphatic carboxylic acid.Preferred catalyzer is an organometallic compound, preferred especially titanic acid ester, iron cpd or tin compound.
Can adopt the mixture of a kind of thermoplastic polyurethane or thermoplastic polyurethane.
Can adopt so-called extrusion machine method, for example adopt many screw extrusion presss to prepare TPU continuously.The composition A that can add TPU simultaneously), B) and dosage C), promptly adopt single stage method, also can add successively, promptly adopt the prepolymer method.At this moment prepolymer can be taked to be interrupted to provide or join continuously in a section of extrusion machine or in an independent upstream prepolymer device and prepare.
Polyolefine is for example polyethylene, polypropylene, poly-1-butylene and polymethylpentene, and polyolefine also can comprise the non-conjugated diene of minor amounts of copolymerized.These polymkeric substance are known, at Roempp showed chemistry encyclopedia (Chemie-lexikon), the 8th edition 1987, the 5 volume, in 3307 pages and narrated these polymkeric substance in the document that the application quotes.
Suitable thermoplastic ethylene's (being total to) polymkeric substance is vinyl aromatic compounds, vinyl cyanide (unsaturated nitrile), (methyl) vinylformic acid (C 1-C 8At least a polymer of monomers in)-alkyl ester, unsaturated carboxylic acid and the olefinically unsaturated carboxylic acid derivatives (for example acid anhydrides and imines).D.1 and (being total to) polymkeric substance D.2 be very suitable,
D.1 50-99 weight part, preferred 60-80 parts by weight of ethylene base aromatics, and/or nuclear substituted vinyl aromatic compounds (for example vinylbenzene, alpha-methyl styrene, p-methylstyrene, right-chlorostyrene), and/or methacrylic acid (C 1-C 4)-alkyl ester (for example methyl methacrylate, Jia Jibingxisuanyizhi) and
D.2 1-50 weight part, preferred 20-40 parts by weight of ethylene base cyanogen (unsaturated nitrile) is as vinyl cyanide, methacrylonitrile and/or (methyl) vinylformic acid (C 1-C 8The derivative (for example acid anhydrides and imines) of)-alkyl ester (for example methyl methacrylate, n-butyl acrylate, the special butyl ester of vinylformic acid) and/or unsaturated carboxylic acid (for example toxilic acid) and/or unsaturated carboxylic acid (for example maleic anhydride and N-phenyl Malaysia imines).
This class (being total to) polymkeric substance is resinoid, thermoplastic and does not contain rubber.
D.1 be vinylbenzene especially preferably and D.2 be the multipolymer of vinyl cyanide.
In addition, alkyl and/or halogen also are preferred at nuclear substituted polystyrene or Alpha-Methyl polystyrene.
These (being total to) polymers are known, can particularly be prepared by emulsion polymerization, suspension polymerization, solution polymerization or mass polymerization effect by the radical polymerization effect.The molecular weight M of these (being total to) polymers W(weight-average molecular weight, measure by scattering of light or by deposition) is preferably 15,000-200,000.
Suitable graftomer is E.1 at E.2 one or more graftomer,
E.1 5-95%, at least a vinyl monomer of preferred 30-80% (weight);
E.2 95-5%, one or more graft bases of preferred 70-20% (weight), its glass transition temp＜10 ℃, preferred＜0 ℃, preferred especially＜-20 ℃.
Graft bases mean particle size (d E.2 50Value), be generally 0.05-5 μ m.
E.1.1 and mixture E.1.2 E.1, preferred monomers is,
E.1.1 50-99 parts by weight of ethylene base aromatics and/or nuclear substituted vinyl aromatic compounds (for example vinylbenzene, alpha-methyl styrene, p-methylstyrene, right-chlorostyrene) and/or methacrylic acid (C 1-C 4) alkane ester (for example methyl methacrylate, Jia Jibingxisuanyizhi) and
E.1.2 1-50 parts by weight of ethylene base cyanogen (unsaturated nitrile, for example vinyl cyanide and methacrylonitrile) and/or (methyl) vinylformic acid (C 1-C 4) derivative (for example acid anhydrides and imines) of alkyl ester (for example, the special butyl ester of methyl methacrylate, methyl acrylate, n-butyl acrylate, vinylformic acid) and/or unsaturated carboxylic acid (for example maleic anhydride and N-phenyl Malaysia imines).
E.1.1, preferred monomer is selected from least a monomer in vinylbenzene, alpha-methyl styrene and the methyl methacrylate, and E.1.2 preferred monomer is selected from least a monomer in vinyl cyanide, maleic anhydride, methyl acrylate and the methyl methacrylate.
E.1.1, particularly preferred monomer is a vinylbenzene, E.1.2 is vinyl cyanide.
E.2, the graft bases that is fit to graft polymerization is for example elastoprene, EP (D) M-rubber, promptly based on ethylene/propene with the rubber of diene, acrylate, urethane, silicone, chloroprene and Ethylene/vinyl acetate rubber also can be arranged.
E.2, preferred graft bases is elastoprene (for example based on divinyl, an isoprene etc.), or the mixture of elastoprene, or elastoprene multipolymer, or itself and other can copolymerization the mixture of monomer (for example according to E.1.1 and E.1.2), condition is composition glass transition temp＜10 E.2 ℃, preferably＜0 ℃, preferred especially＜-10 ℃.
Preferred especially pure polybutadiene rubber.
Particularly preferred polymkeric substance is, for example at German Patent-OS 2 035 390 (=United States Patent (USP)-PS 3 644 574), or German Patent-OS 2 248 242 (=English Patent-PS 1 409275), or at Ullmann Enzyklop  die der Technischen Chemie (Liv Ullmann industrial chemistry encyclopaedia), vol.19 (1980), the abs polymer (ABS of emulsion polymerization, mass polymerization and suspension polymerization) described in p.280 reaching thereafter.
Graftomer is by the radical polymerization preparation, for example by emulsion polymerization, suspension polymerization, solution polymerization or mass polymerization, preferably by the emulsion polymerization.
According to suitable acrylic elastomer E.2, preferably by alkyl acrylate, also can contain by E.2 up to other of 40% (weight) can polymeric ethylenically unsaturated monomer.Preferably can comprise C by the polymeric acrylate 1-C 8-alkyl ester, for example methyl, ethyl, butyl, n-octyl and 2-(ethyl hexyl) ester; The haloalkyl ester, preferred halo-C 1-C 8-alkyl ester, for example vinylformic acid chloroethene ester; With these monomeric mixtures.
For crosslinked, make monomer copolymerization with an above polymerizable double bond.The example of preferred cross-linking monomer is the unsaturated monocarboxylic acid of 3-8 carbon atom and the unsaturated monohydroxy-alcohol of 3-12 carbon atom, or with the ester class of saturated polyol generation, for example Ethylene glycol dimethacrylate, allyl methacrylate with 2-4 OH base and 2-20 carbon atom; Many unsaturated heterocyclic compounds, for example cyanuric acid trivinyl ester and cyanuric acid triallyl ester; Polyfunctional vinyl compound, for example Vinylstyrene and trivinylbenzene; Also can be tricresyl phosphate allyl ester and phthalic acid diallyl ester.
Preferred cross-linking monomer is allyl methacrylate, Ethylene glycol dimethacrylate, phthalic acid diallyl ester and the heterogeneous ring compound with at least 3 olefinic unsaturated groups.
Particularly preferred cross-linking monomer is monomer-cyanuric acid triallyl ester, tricarbimide triallyl ester, three acryloyls, six hydrogen-in addition-triazine, the triallyl benzene of band.By graft bases E.2 the amount of cross-linking monomer is preferably 0.02-5%, preferred especially 0.05-2% (weight).
Under the situation of the ring-type cross-linking monomer with at least three olefinic unsaturated groups, it is favourable that restriction graft bases amount E.2 is lower than 1% (weight).
Except acrylate, E.2 the preparation graft bases also can use preferred " other " can the polymeric ethylenically unsaturated monomer be for example vinyl cyanide, vinylbenzene, alpha-methyl styrene, acrylamide, vinyl-C 1-C 6-alkyl oxide, methyl methacrylate and divinyl.As graft bases preferred acrylic elastomer E.2 is that gel content is the emulsion polymer of at least 60% (weight).
According to the graft bases that is more suitable for E.2, be at the silicone rubber described in German Patent-OS 3 704 657,3,704 655,3 631 540 and 3 631 539 with grafting activity site.
Under 25 ℃, measure graft bases gel content (M.Hoffmann, H.Kr mer, R.Kuhn, polymer analysis (Polymeranalytik) I and II, Georg Thieme press, Stuttgart, 1977) E.2 with The suitable solvent
Mean particle size d 50, be that 50% (weight) particulate diameter is respectively arranged down thereon.Mean particle size can adopt the ultracentrifugation measuring method measure (W.Scholtan, H.Lange, colloid and polymkeric substance magazine (Kolloid.Z, und Z.Polymere) 250 (1972), 782-1796).
For example, in European patent-A 164 767, narrated the polyphenylene ether under situation of the present invention.
Filler and stiffeners, particularly mineral filler can be mixed with polyketone and polyketone mixture.Filler that can adopt and stiffeners are for example kaolin, talcum, wollastonite, glass fibre (comprising long glass fibres, successive glass fibre, glass fabric and glass yarn felt), granulated glass sphere, lime carbonate, carbon fibre, arylamide fiber or mica, natural fiber or its mixture.
By total mixture, the amount of filler that adopts is up to 50% (weight) usually, preferred 5-30% (weight).
The moulding compound of polyketone and polyketone mixture can comprise conventional additive, for example lubricant, releasing agent, nucleator, static inhibitor, stablizer, pigment and pigment.
For the moulding compound that obtains to conduct electricity, can add carbon black, carbon fiber, the graphite of conduction, polymkeric substance, steel fiber and other conventional additive of conduction, to improve electric conductivity.
The exterior part of auto parts machinery of the present invention or car body can adopt conventional plastic processing technology by polyketone or polyketone mixture, for example injection molding, extrude, the combination of thermoforming, deep-draw, compacting, welding, die, sinter, blowing and gas injection technique or these technology makes.
For this reason, adopt known method, make polyketone randomly with its mixing element, randomly mix with filler, stiffeners and/or the additive of routine, both can be with the form of this mixture, adopt conventional plastic processing technology, directly make work in-process of the present invention (for example plate, film and section bar) or molded parts (auto parts machinery), also can at high temperature preferably under 200-350 ℃, adopt conventional equipment, for example extrusion machine, interior kneader, twin axle screw are with its melting mixing, make thermoplastic moulding compound, then, for example granulation.By the granulated material that polyketone or polyketone mixture are formed, the conventional plastic processing technology of having listed above the employing is further processed, and makes work in-process of the present invention (for example plate, film and section bar) or molded parts (auto parts machinery).Adopt routine techniques, work in-process are further processed in for example thermoforming, make auto parts machinery of the present invention.
Have been found that the auto parts machinery that the present invention is made by polyketone or polyketone mixture, can with other material, for example metal or plastics the combination.After the auto parts machinery japanning, can be directly on the moulding compound of forming by polyketone or polyketone mixture, and/or obtain enamelled coating uniting on the material of use.
The mixture that forms by polyketone, mixing element, filler, stiffeners and/or additive of the present invention, or by polyketone, or the moulding compound of polyketone mixture formation, or by polyketone, or the work in-process of polyketone mixture formation, also can adopt routine techniques to connect or make up several parts or parts, for example adopt coextrusion, back plated film, interlayer injection moulding, back compacting, back die and by subchassis injection moulding, multicomponent injection moulding, welding, compacting, bonding, fusion, tighten or clamp to combine with other material or to be used to make auto parts machinery separately.
Be listed below as preferred auto parts machinery: splash pan, collision bumper, back door, luggage-boot lid, side door involucrum, engine shield, car ceiling, radiator grill, external mirror.
Embodiment
Use following ingredients in an embodiment:
A) polyketone:
The trimer that the straight chain that carbon monoxide, ethene and propylene are formed is staggered, (Carilon DPP1000, Britain, London, the international chemical company limited of shell)
B) polyketone/ABS
The Carilon of 95% (weight) DP P1000 and 5% ABS
Polyketone:
Carilon DP P1000, the international chemical company limited of shell
The ABS graft rubber:
A kind of employing rubber stock (rubber (polyhutadiene) that 50% (weight) exists with the latex form, average particulate diameter d 50Be 280nm, gel content is the rubber (polyhutadiene) that 53% (weight) and 50% (weight) exist with the latex form, average particulate diameter d 50Be 420nm, gel content is 85% (weight)), the graft rubber that the emulsion polymerization that causes by Potassium Persulphate prepares, its rubber content is 50% (weight), the content of graft shell is 50% (weight), and graft shell is by 27 parts of (weight) vinyl cyanide and 73 parts of (weight) cinnamic mixture graft polymerization synthetic.
Polyketone and rubber are mixing in ZSK32 type extrusion machine under 220-240 ℃.
C) polyketone/TPU:
The Carilon of 95% (weight) The TPU of DP P1000 and 5% (weight)
Polyketone:
Carilon DP P1000 (seeing A)
Thermoplastic urethane (TPU):
Desmopan 385, Germany, Li Fokesen, Bayer AG
(based on polytetramethylene glycol-1,4-adipic acid ester, butyleneglycol 1,4, methylene diphenyl diisocyanate)
Polyketone and TPU are mixing in ZSK 32/1 type extrusion machine under 220-240 ℃.
D)PBT：
Pocan 1300, Germany, Li Fokesen, Bayer AG
E) PPO/PA (polyphenylene oxide/polyamide compound):
Noryl GTX964, the U.S., Field now, general electronic corporation plastics
F) mixture of improvement tough
Pocan KU 2-7912, Germany, Li Fokesen, Bayer AG
The moulding bodies that experiment needs is to adopt Arburg320-210-500 type injector,
Under the molding temperature of thermoplastics manufacturer recommendation, prepare.
In the torque oscillation experiment as temperature function, the RDSII type instrument that adopts Rheometrics company to provide is under the survey frequency of 1Hz, to 80 * 10 * 4mm 3Coupon, carry out the dynamic mechanical of comprehensive shear modulus and measure.Shear modulus G ' can provide relevant inflexible data, available its measuring as thermotolerance and dimensional stability.Shear modulus G ' under corresponding baking vanish temperature is about 80-100MPa, think this value indeformable to the auto parts machinery baking vanish be enough.
Run through in the experiment at twin axle,, the behavior of 60mm disk when suffering shock stress that 3mm is thick tested according to ISO6603-2.
In pulling experiment, measure the Young's modulus of dumbbell specimen according to ISO527.2.
Adopt standard method well known by persons skilled in the art, the test varnishability.
With the naked eye assess the surface of moulded parts.
Table 1
Embodiment 1 Embodiment 2 Embodiment 3 Comparative Examples 1 Comparative Examples 2 Comparative Examples 3
Polyketone Polyketone/ABS Polyketone/TPU ????PBT ????PPO/PA The PC/PBT mixture
Shear modulus G ' under 160 ℃ [MPa] ????176 ??102 ????122 ????75 ????208 ????14
Shear modulus G ' under 180 ℃ [MPa] ????129 ??80 ????95 ????57 ????178 ????10
Ductility transmition in the twin shaft piercing test/fragility transformation [℃] About-30 About-35 About-35 About 0 About-15 About-35
Young's modulus under 22 ℃ [MPa] ????1950 ??1800 ????1400 ????2700 ????2000 ????2200
Paintability Be Be Be Be Be Be
The surface The A level The A level The A level The A level The A level The A level
Polyketone and PBT are the thermoplasticss of partial crystallization.Though the glass transition temp of polyketone is about 12 ℃, thereby is lower than room temperature, rigidity at high temperature (shear modulus) but is higher than the thermoplastics of PBT and other comparable partial crystallization basically.Different with the thermoplastics of other typical partial crystallization, because being used to insert the auto parts machinery of online and online japanning, polyketone has enough thermotolerances.Compare with the PPO/PA mixture with PBT, the low-temperature impact toughness of polyketone is much better, and its toughness/brittle transformation is at-30 ℃ approximately.Through improving the PC/PBT mixture of impelling strength, be a kind of mixture systems that typically is used for the auto parts machinery of off-line japanning, have extraordinary low-temperature flexibility, but to inserting online or online japanning, its thermotolerance is not enough at all.The example of polyketone/ABS and polyketone/TPU shows, has also kept polyketone to inserting the advantageous property of online and online japanning accessory in the polyketone mixture.

Claims (6)

1. auto parts machinery based on the thermoplasticity polyketone.
One kind based on the thermoplasticity polyketone and with the auto parts machinery of the mixture of other thermoplastics, other thermoplastics is selected from least a in polyalkylene terephthalate, thermoplastic ethylene's base (being total to) polymkeric substance, graftomer, polyolefine and/or the thermoplastic elastomer.
3. according to the auto parts machinery that can insert online japanning of claim 1 and 2.
4. according to the auto parts machinery of the online japanning of energy of claim 1 and 2.
5. according to the auto parts machinery of one of aforementioned claim, wherein thermoplasticity polyketone and composition thereof comprises filler and/or stiffeners and also can have and is selected from additive at least a in lubricant, releasing agent, nucleator, static inhibitor, stablizer, pigment and the pigment, and the additive that improves electric conductivity.
6. the thermoplasticity polyketone also can mix the application in making auto parts machinery with other thermoplastics and other additive.
CN99811855A 1998-10-07 1999-09-24 Body add-on parts based on thermoplastic polyketones Pending CN1322221A (en)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE19846051A DE19846051A1 (en) 1998-10-07 1998-10-07 Body attachments based on thermoplastic polyketones
DE19846051.1 1998-10-07

Publications (1)

Publication Number Publication Date
CN1322221A true CN1322221A (en) 2001-11-14

Family

ID=7883603

Family Applications (1)

Application Number Title Priority Date Filing Date
CN99811855A Pending CN1322221A (en) 1998-10-07 1999-09-24 Body add-on parts based on thermoplastic polyketones

Country Status (8)

Country Link
EP (1) EP1117724A1 (en)
JP (1) JP2002526330A (en)
KR (1) KR20010080019A (en)
CN (1) CN1322221A (en)
AU (1) AU6196199A (en)
BR (1) BR9914316A (en)
DE (1) DE19846051A1 (en)
WO (1) WO2000020486A1 (en)

Cited By (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN106243677A (en) * 2016-08-24 2016-12-21 五行科技股份有限公司 A kind of flame retardant type fiberglass reinforced polyketone composite that can be used for automotive fuel oil system
CN106661322A (en) * 2014-07-18 2017-05-10 株式会社晓星 Polycarbonate resin composition and optical molded article comprising same
CN107513263A (en) * 2017-10-19 2017-12-26 威海联桥新材料科技股份有限公司 A kind of thermoplastic elastomer (TPE) gasket material and its production method
CN109354857A (en) * 2018-11-09 2019-02-19 晋江瑞碧科技有限公司 Fretting map POK composite material and preparation method and purposes
CN110684189A (en) * 2019-11-11 2020-01-14 黄河三角洲京博化工研究院有限公司 Polyketone synthesis method
CN111607077A (en) * 2020-06-24 2020-09-01 黄河三角洲京博化工研究院有限公司 Preparation method of polyketone

Families Citing this family (12)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE10054433B4 (en) * 2000-10-26 2009-12-17 Volkswagen Ag Method for painting a body part
DE102006039972B4 (en) * 2006-08-25 2015-10-22 Bayerische Motoren Werke Aktiengesellschaft Starting component and method for producing a component made of thermoplastic material
KR100972357B1 (en) * 2009-02-09 2010-07-26 주식회사 상신산업 Expandable tube type rock bolt
KR101620568B1 (en) * 2014-07-18 2016-05-13 주식회사 효성 Polyketone article and snow chains
KR101734888B1 (en) * 2014-11-19 2017-05-24 주식회사 효성 Polyketoen composition comprising p-aramid
KR101664926B1 (en) * 2014-11-19 2016-10-11 주식회사 효성 Polyketone composition comprising polyester
ES2676498T3 (en) * 2015-11-13 2018-07-20 Ems-Patent Ag Flame retardant aliphatic polyketonic materials, molding bodies derived from them as well as procedures for their production
KR101777562B1 (en) 2015-11-27 2017-09-13 (주)휴이노베이션 Flame Retardant Composition Having Eco-friendly and Excellent Low-smoke Characteristics and Comprising Polyketone Resin and Polyalkylene-carbonate Resin
DE102016013868A1 (en) * 2016-11-28 2018-05-30 Carl Freudenberg Kg Polymer mixture for seals
KR101888071B1 (en) 2017-04-20 2018-08-14 주식회사 효성 Polyketone resin composition having improved processing stability and mechanical properties
FR3077013B1 (en) * 2018-01-24 2023-12-15 Aptar France Sas FLUID PRODUCT DISTRIBUTION DEVICE.
KR101894810B1 (en) * 2018-06-15 2018-09-04 주식회사 효성 Blend Comprising Polyketone and ABS and Method for Preparing the Same

Family Cites Families (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
ATE106927T1 (en) * 1987-12-21 1994-06-15 Shell Int Research POLYKETONE POLYMER COMPOSITION.
US4921897A (en) * 1989-03-31 1990-05-01 Shell Oil Company Flame retardant composition containing zinc borate
US5369180A (en) * 1991-08-22 1994-11-29 Shell Oil Company Miscible polyketone polymer blend
US5166252A (en) * 1991-08-29 1992-11-24 Shell Oil Company Polyketone blend having improved mechanical properties
ZA964914B (en) * 1995-06-12 1997-01-08 Shell Int Research Catalyst composition and process for the preparation of copolymers of carbon monoxide and an olefinically unsaturated compound
DE19817812A1 (en) * 1998-04-21 1999-10-28 Bayer Ag Thermoplastic molding composition, useful for production of plugs, sockets, automotive parts and equipment casings
DE19817809A1 (en) * 1998-04-21 1999-10-28 Bayer Ag Molding compositions, useful for production of tubing and containers for fuel, fuel pumps and cable sheathing

Cited By (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN106661322A (en) * 2014-07-18 2017-05-10 株式会社晓星 Polycarbonate resin composition and optical molded article comprising same
CN106661322B (en) * 2014-07-18 2020-07-07 晓星化学(株) Polyketone resin composition having excellent oil resistance
CN106243677A (en) * 2016-08-24 2016-12-21 五行科技股份有限公司 A kind of flame retardant type fiberglass reinforced polyketone composite that can be used for automotive fuel oil system
CN107513263A (en) * 2017-10-19 2017-12-26 威海联桥新材料科技股份有限公司 A kind of thermoplastic elastomer (TPE) gasket material and its production method
CN107513263B (en) * 2017-10-19 2020-08-04 威海联桥新材料科技股份有限公司 Thermoplastic elastomer gasket material and production method thereof
CN109354857A (en) * 2018-11-09 2019-02-19 晋江瑞碧科技有限公司 Fretting map POK composite material and preparation method and purposes
CN110684189A (en) * 2019-11-11 2020-01-14 黄河三角洲京博化工研究院有限公司 Polyketone synthesis method
CN111607077A (en) * 2020-06-24 2020-09-01 黄河三角洲京博化工研究院有限公司 Preparation method of polyketone

Also Published As

Publication number Publication date
JP2002526330A (en) 2002-08-20
WO2000020486A1 (en) 2000-04-13
KR20010080019A (en) 2001-08-22
BR9914316A (en) 2001-08-07
DE19846051A1 (en) 2000-04-13
AU6196199A (en) 2000-04-26
EP1117724A1 (en) 2001-07-25

Similar Documents

Publication Publication Date Title
CN1322221A (en) Body add-on parts based on thermoplastic polyketones
CN1200974C (en) Polymer blend of low temp. impact strength
CN1129649C (en) Compatibilized blends of thermoplastic elastomer and polyolefin
EP0400890B1 (en) Method for producing thermoplastic elastomer composition
CN1132224A (en) Polymide-based flame-retardant thermoplastic compositions and their application to covering of electrical cables
CN1733817A (en) Thermoplastic polyurethanes
CN1757673A (en) Polybutylene terephthalate resin composition
CN1272514A (en) Aliphatic melt-cohesible thermoplastic polyurethane moulding composite with improved performance
JP5581606B2 (en) Resin composition having excellent moldability and molded product thereof
CN1961038A (en) Use of thermoplastic composition comprising polyether-block copolyamides as additive
CN1278279A (en) Diol latex compositions
CN1128845C (en) Thermoplastics with improved flexibility and transparency
JP2002097378A (en) Filler-containing antistatic resin composition
CN1495210A (en) Continuous preparation of thermoplastic workable polyurethane
CN1533338A (en) Composite skin for instrument panel and other parts of vehicle passenger compartment, method for making same, and composition for preparing same and method for producing it
CN1258567C (en) Polyamide thermoplastic compsns. with improved impact strength properties
CN1729233A (en) Be used to improve the enriched material of the surperficial adhesion characteristic of polyacetal-based composition and use thereof in packaging
CN1753942A (en) Compatibilizing agent for engineering thermoplastic/polyolefin blend
CN1125120C (en) Thermoplastic resin composition contg. hard dispersion phase
CN1569993A (en) Method for preparing composite coating film
JP3899178B2 (en) Flame retardant resin composition
CN1161356A (en) Compositions based on polyamides and on polyolefins which are flexurally very flexible
JP5500033B2 (en) Polycarbonate-polyester composite resin composition and molded article
CN1742045A (en) Impact-strength-modified polymer compositions
CN101074309A (en) Thermoplastic resin composition, thermoplastic resin composition for exterior automotive molding, exterior automotive molding, and process for producing exterior automotive molding

Legal Events

Date Code Title Description
C06 Publication
PB01 Publication
C02 Deemed withdrawal of patent application after publication (patent law 2001)
WD01 Invention patent application deemed withdrawn after publication