CN1225935A - Thermoplastic olefin compositions containing maleic anhydride-modified polymers and capable of directly painting - Google Patents
Thermoplastic olefin compositions containing maleic anhydride-modified polymers and capable of directly painting Download PDFInfo
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Abstract
Directly paintable polymer compositions contain (1) a thermoplastic olefin, (2) a maleic anhydride-grafted propylene homopolymer or random copolymer, (3) a maleic anhydride-grafted olefin polymer material, (4) functionalized polymer that reacts with the maleic anhydride groups of the grafted polymers, and optionally, (5) a maleic anhydride-grafted ethylene polymer. The amount of (2) + (3) or (2) + (3) + (5) is at least 16 parts but less than 27 parts per hundred parts of the thermoplastic olefin.
Description
The present invention relates to comprise the Themoplastic olefin compositions of maleic anhydride-modified polymers and functionalized polymeric additive.
Thermoplastic olefin (TPO) is the uncrosslinked blend of olefin polymer and polyolefin elastomer.They can make through polymerization through physical mixed or in reactor in internal mixer.These materials are not paintable or coating, reason be paint or coating by with such as the non-constant of binding property of polyolefinic non-polar material such as urethane, acrylic polymer, the polar material of epoxy or melamine is formed.The general tackifier that use are as the transition layer between TPO ground and the coating.This additional step has increased the expense of product, and coating is very short-life.
European patent application 662,496 have disclosed a kind of paintable or printable polymer composition of being made up of polyolefine or polyolefine/rubber blend and at least a polymeric additive of 0.1-10 weight %, described additive is (a) by the polyolefine of unsaturated acid, ester or anhydride modification or polyester and (b) amine, hydroxyl or alkoxy end-capped polyoxyethylene, the reaction product of polyoxypropylene or both multipolymers, the reaction product of end capped poly-(oxyethane) glycol of for example maleic anhydride-modified Poly Propylene Wax and methoxyl group.
European patent application 634,424 has disclosed the blend of a kind of polypropylene and maleation polypropylene and polyetheramine reaction product.Compare with the blend of maleation polypropylene reaction product with polypropylene with polypropylene, above-mentioned blend demonstrates improved paintability, improved shock resistance and good moulding flowability.Yet, EP662,496 and EP 634,424 disclosed in composition all be poor on wearing quality.
By weight, composition of the present invention comprises following component:
(1) 100 part of thermoplastic olefin that comprises following (a)-(d):
(a) about 60% isotactic index of about 10%-is greater than 90% alfon, or propylene content greater than 85% and isotactic index greater than 85% comprise ethene and/or C
4-8The crystalline propylene copolymer of alpha-olefin;
(b) about 30%-about 60% randomly comprises the amorphous ethylene-propylene or the ethylene-butene copolymer component of about 10% diene of about 1%-, and described copolymer component at room temperature is dissolved in dimethylbenzene and comprises the ethene of about 30%-about 70%;
(c) be insoluble to dimethylbenzene under about 20% room temperature of about 2%-and comprise greater than 75% but less than the semi-crystalline ethylene-propylene or the ethylene-butene copolymer of 92% ethene; With
(d) about 20% density of about 5%-is 0.91-0.96g/cm
3, melt index is the ethene polymers of 0.1-100g/10min;
(2) to be about 2%-about 5% for about 8 parts-Yue 14 parts of maleic anhydride content of per 100 parts of thermoplastic olefins, molecular weight M
nThe maleic anhydride-modified alfon or the ethylene/propylene olefinic random copolymer that are about 2500-about 25,000;
(3) 14 parts of about 5 parts of per 100 parts of thermoplastic olefins-Yue be selected from following (a)-(b) maleic anhydride content at least 0.3% but less than 3% maleic anhydride grafted olefin polymer material:
(a) comprise ethylene-propylene or ethylene-butene copolymer rubber, randomly comprise the maleic anhydride grafted polyolerin elastomer of about 10% diene of about 0.5%-, described copolymer rubber comprise about 30%-about 70% ethene and
(b) maleic anhydride grafted amphoteric polymeric material, wherein amphoteric polymeric material mainly comprises following component (ⅰ)-(ⅲ):
(ⅰ) about 50% isotactic index of about 10%-is about the alfon of 80%-about 99%, or is selected from the multipolymer of following (a)-(c), (a) propylene and ethene, (b) propylene, ethene and CH
2=CHR alpha-olefin, wherein R is C
2-8The straight or branched alkyl and (c) propylene and as above-mentioned (ⅰ) (b) in defined alpha-olefin, this multipolymer comprises the propylene of about 85%-about 99%, and isotactic index is about 80%-about 98%;
(ⅱ) about 3%-about 20% records degree of crystallinity by dsc (DSC) and is about the hypocrystalline of 20%-about 60%, the copolymer component of line style basically, and wherein multipolymer is selected from following (a)-(c), (a) contains ethene and propylene greater than 50% ethene; (b) contain about 10% alpha-olefin of about 1%-and greater than the ethene of 50% to 98% ethene and alpha-olefin, propylene and as above-mentioned (ⅰ) (b) in defined alpha-olefin; (c) contain greater than the ethene of 50% to 98% alpha-olefin and as above-mentioned (ⅰ) (b) in defined alpha-olefin, described multipolymer is insoluble to dimethylbenzene under room temperature or envrionment temperature; With
(ⅲ) about 40%-about 80% is selected from the copolymer component of following (a)-(c) multipolymer, (a) ethene and propylene, and wherein multipolymer contains 20%-less than 40% ethene; (b) ethene, propylene and as above-mentioned (ⅰ) (b) in defined alpha-olefin, wherein to be about 1%-about 10% for the amount of alpha-olefin, the amount of ethene and alpha-olefin is that 20%-is less than 45%; (c) comprise 20%-less than 45% alpha-olefin and randomly comprise about 10% diene of about 0.5%-ethene and as above-mentioned (ⅰ) (b) defined alpha-olefin, copolymer component (ⅲ) is dissolved in dimethylbenzene at ambient temperature, its limiting viscosity is about about 3.0 dl/g of 1.7-, wherein in the total amount of olefin polymer compositions, component (ⅱ) and total amount (ⅲ) are about 65%-about 80%, it is about 0.3 that the weight ratio of component (ⅱ)/(ⅲ) is about 0.1-, ethene or C in component (ⅱ)+(ⅲ)
4-8The total content of alpha-olefin or their mixture is less than 50%;
(4) be selected from following (a)-(c), with (2), the functionalized polymeric of the acid anhydride radical reaction of (3) and (5) (if the words that exist):
(a) the about 6 parts of end capped polyalkylene glycols of amine of per 100 parts of about 2.7-of thermoplastic olefin;
(b) the about 6 parts of hydroxylation polymkeric substance that are selected from following (ⅰ)-(ⅲ) of per 100 parts of about 2-of thermoplastic olefin:
(ⅰ) hydroxylation polyethylene,
(ⅱ) the hydroxylation polybutene and
(ⅲ) hydroxylated polybutadiene; With
(c) mixture of per 100 parts of about 2-of thermoplastic olefin about 6 parts (a)+(b), wherein (a) and ratio (b) are about 0.1-about 0.9; With optional
(5) about 4 parts-Yue 15 parts of maleic anhydride content of per 100 parts of thermoplastic olefins are about 2%-about 13% and molecular weight M
nThe maleic anhydride grafted ethene polymers that is about 500-about 3000,
In wherein per 100 parts of thermoplastic olefins, (2)+(3) or (2)+(3)+(5) are at least 16 parts but less than 27 parts, and when having maleic anhydride grafted polyethylene, (3)+(5) are equal to or greater than 10 parts in per 100 parts of thermoplastic olefins.
Injection-molded parts can directly apply with polarity paint or coating as the bumper of being made by this composition, does not need tackify mixture layer between thermoplastic olefin surface and paint.
The component of the present composition (1) is for comprising the thermoplastic olefin of following component (by weight):
(a) about 10%-is about 60%, and about 50% isotactic index of better about 20%-is preferably the alfon of 95%-98% greater than 90%, or propylene content greater than 85% and isotactic index greater than 85% comprise ethene and/or C
4-8The crystalline propylene copolymer of alpha-olefin;
(b) about 30%-about 60%, better about 30%-about 50% randomly comprises the amorphous ethylene-propylene or the ethylene-butene copolymer component of about 10% diene of about 1%-, and described copolymer component at room temperature is dissolved in dimethylbenzene and comprises the ethene of about 30%-about 70%;
(c) about 2%-is about 20%, is insoluble to dimethylbenzene under about 15% room temperature of better about 7%-and comprises greater than 75% but less than the semi-crystalline ethylene-propylene or the ethylene-butene copolymer of 92% ethene; With
(d) about 5%-is about 20%, and about 15% density of better about 7%-is 0.91-0.96g/cm
3, melt index is 0.1-100g/10min, the ethene polymers of the about 50g/10min of better about 15-.Alathon is better.Yet, also can use to comprise 8% or the multipolymer of alpha-olefin comonomer still less.
Thermoplastic olefin generally makes through the sequential polymerization of three steps at least.Component (a) can prepare in first reactor, component (b) and (c) in second reactor, prepare, and component (d) prepares in the 3rd reactor.Perhaps, component (d) can prepare in second reactor, and component (b) and (c) in the 3rd reactor, prepare.Polymerizing condition and polymerizing catalyst be at United States Patent (USP) 5,302, more detailed description arranged in 454, its content at this with reference to quoting.Perhaps, can separately prepare four components, then blend together.Sequential polymerization is better.
Used C in the preparation thermoplastic olefin
4-8Alpha-olefin for example comprises butene-1; Amylene-1; Hexene-1; 4-methylpentene-1, and octene-1.
When having diene, it is generally divinyl; 1, the 4-hexadiene; 1,5-hexadiene, or ethylidene norbornene.
The amount of thermoplastic olefin is 100 weight parts.
It is about 4% that component (2) is that maleic anhydride grafted alfon or ethylene content are about 0.5%-, better is about the ethylene/propylene olefinic random copolymer of 1%-about 3%.Alfon is better.It is about 5% that the maleic anhydride content of polymkeric substance is about 2%-, and it is about 4% better to be about 3%-, its molecular weight M
nIt is about 25,000 better to be about 2500-, preferably is about 3000-about 10,000.In per 100 parts of thermoplastic olefins, the amount of component (2) is about about 14 parts of 8-, better is about about 12 parts of 10-.
Component (3) is the maleic anhydride grafted olefin polymer material that is selected from following (a)-(b):
(a) comprise ethylene/propene or ethylene/butylene copolymers rubber, it is about 10% randomly to comprise about 0.5%-, the maleic anhydride grafted polyolerin elastomer of about 6% diene of better about 2%-, and described copolymer rubber comprises about 30%-about 70%, better the ethene of about 40%-about 60% and
(b) maleic anhydride grafted amphoteric polymeric material, wherein amphoteric polymeric material mainly comprises following component (ⅰ)-(ⅲ):
(ⅰ) about 50% isotactic index of about 10%-is about the alfon of 80%-about 99%, or is selected from the multipolymer of following (a)-(c), (a) propylene and ethene, (b) propylene, ethene and CH
2=CHR alpha-olefin, wherein R is C
2-8The straight or branched alkyl and (c) propylene and as above-mentioned (ⅰ) (b) in defined alpha-olefin, this multipolymer comprises the propylene of about 85%-about 99%, and isotactic index is about 80%-about 98%;
(ⅱ) about 3%-about 20% records degree of crystallinity by dsc (DSC) and is about the hypocrystalline of 20%-about 60%, the copolymer component of line style basically, and wherein multipolymer is selected from following (a)-(c), (a) contains ethene and propylene greater than 50% ethene; (b) contain about 10% alpha-olefin of about 1%-and greater than the ethene of 50% to 98% ethene and alpha-olefin, propylene and as above-mentioned (ⅰ) (b) in defined alpha-olefin; (c) contain greater than the ethene of 50% to 98% alpha-olefin and as above-mentioned (ⅰ) (b) in defined alpha-olefin, described multipolymer is insoluble to dimethylbenzene under room temperature or envrionment temperature; With
(ⅲ) about 40%-about 80% is selected from the copolymer component of following (a)-(c) multipolymer, (a) ethene and propylene, and wherein multipolymer contains 20%-less than 40% ethene; (b) ethene, propylene and as above-mentioned (ⅰ) (b) in defined alpha-olefin, wherein to be about 1%-about 10% for the amount of alpha-olefin, the amount of ethene and alpha-olefin is that 20%-is less than 45%; (c) comprise 20%-less than 45% alpha-olefin and randomly comprise about 10% diene of about 0.5%-ethene and as above-mentioned (ⅰ) (b) defined alpha-olefin, copolymer component (ⅲ) is dissolved in dimethylbenzene at ambient temperature, its limiting viscosity is about about 3.0 dl/g of 1.7-, wherein in the total amount of olefin polymer compositions, component (ⅱ) and total amount (ⅲ) are about 65%-about 80%, it is about 0.3 that the weight ratio of component (ⅱ)/(ⅲ) is about 0.1-, ethene or C in component (ⅱ)+(ⅲ)
4-8The total content of alpha-olefin or their mixture is less than 50%.
It is about 40% that the amount of component (ⅰ) better is about 10%-, preferably is about 20%-about 35%.When (ⅰ) was alfon, isotactic index better was about 85%-about 98%.When (ⅰ) was multipolymer, the amount of propylene better was about 90%-about 99% in the multipolymer.
The amount of component (ⅱ) better is about 7%-about 15%.The degree of crystallinity that is recorded by DSC generally is about 20%-about 60%.Usually, the content of ethene or alpha-olefin or when the both uses the amount of the mixture of ethene and alpha-olefin better be about 80%-about 95% greater than 55% to 98%.
The amount of component (ⅲ) better is about 50%-about 70%.Better to be about 20%-about 38% for the content of the content of ethene or alpha-olefin or ethene and alpha-olefin in the component (ⅲ), preferably is about 25%-about 38%.
Component (3) is available Ziegler-Natta catalyst (a), metalloscene catalyst or mixed catalyst preparation, and it can be amorphous or is comprised the degree of crystallinity of about 1%-about 10% by dsc measurement.
(b) there is at least one melting peak on 120 ℃ the temperature being higher than by dsc measurement component (3), and on-10 ℃ to-35 ℃ temperature, has at least one peak with respect to glass transition.In addition, the modulus in flexure of these materials is generally 20-100MPa less than 150MPa; Yield tensile strength is 10-20MPa; Extension at break is greater than 400%; Tensile set when 75% strain is 20%-50%; Shore D hardness is 20-35; Haze value is preferably less than 35% less than 40%, and carries out izod (Izod impact) the test time can not rupture (no fragility impact fracture) in the time of-50 ℃.
Suitable formula CH
2The alpha-olefin of=CHR for example comprises butene-1; Amylene-1; 4-methylpentene-1; Hexene-1, and octene-1.
When there is diene in component (3) in (a), it is generally 1,4-hexadiene, ethylidene norbornene or Dicyclopentadiene (DCPD).When there is diene in component (3) in (b), it is generally divinyl; 1, the 4-hexadiene; 1,5-hexadiene or ethylidene norbornene.
Component (3) (b) can be through comprising the polymerization process preparation of at least two steps, wherein in the first step, make propylene, or propylene and ethene or alpha-olefin, or propylene, ethene and alpha-olefine polymerizing generate component (ⅰ), in following step, make ethene and propylene or alpha-olefin, or propylene, the mixture of ethene and alpha-olefin and optional diene carries out polymerization and generates component (ⅱ) and (ⅲ).
Polymerization can use separately reactor in liquid phase, and gas phase or gas-liquid are carried out in mutually, and all can partial or continuous mode carry out.For example, can use liquid propene as thinner polymeric component (ⅰ), vapour phase polymerization component (ⅱ) and (ⅲ) does not need intermediate steps except the propylene partly degassed.The preparation of amphoteric polymeric material is at United States Patent (USP) 5,212, more detailed description arranged in 246, its content at this with reference to quoting.
In per 100 parts of thermoplastic olefins, the amount of olefin polymer material (3) is about about 14 parts of 5-, better is about 8-12 part.The maleic anhydride content of olefin polymer material is at least 0.3%, but less than 3%, is preferably less than 1%, is preferably less than 0.8%.The amount of maleic anhydride is equal to or greater than 3% will obtain gel, poor adhesion and poor durability.
Component (4) be can with component (2), the functionalized polymeric of the maleic anhydride radical reaction in (3) and (5) (if exist words), it is selected from the end capped polyalkylene glycol of (a) amine, polyoxyethylene glycol for example, polypropylene glycol, the multipolymer of polyoxyethylene glycol and polypropylene glycol, poly-(1, the 2-butyleneglycol) and poly-(1, the 4-butyleneglycol) and (b) be selected from the hydroxylation polymkeric substance of following (ⅰ)-(ⅲ), (ⅰ) hydroxylation polyethylene, (ⅱ) hydroxylation polybutene and (ⅲ) hydroxylated polybutadiene.The end capped polyethylene oxide of amine is better.
When existing component (4) (a), in per 100 parts of thermoplastic olefins, its consumption is about about 6 parts of 2.7-, better is about about 4 parts of 2.8-, and when existing component (4) (b), in per 100 parts of thermoplastic olefins, its consumption is about about 6 parts of 2-, better is about about 5 parts of 3-.In per 100 parts of thermoplastic olefins, the consumption of mixture (a)+(b) also is about about 6 parts of 2-, (a) is about 0.1-about 0.9 with (b) ratio.
It is about 13% that optional components (5) is that maleic anhydride content is about 2%-, better is about the maleic anhydride grafted ethene polymers of 3%-about 6%.Alathon is better.Yet, also can use to contain 10% or the multipolymer of alpha-olefin comonomer still less.Polyvinyl molecular weight M
nIt is about 3000 better to be about 500-, preferably is about 650-about 2500; Fusing point better is about 90 ℃-Yue 129 ℃, preferably is about 92 ℃-Yue 126 ℃, and better to be about 20-about 1000 for the viscosity of (ASTM D-88) in the time of 149 ℃, preferably is about about 500 SUS of 100-(Saybolt seconds universal).When using component (5), its consumption is about about 15 parts of 4-in per 100 parts of thermoplastic olefins, better is about about 10 parts of 5-, and the amount of (3)+(5) is equal to or greater than 10 parts in per 100 parts of thermoplastic olefins.
In per 100 parts of thermoplastic olefins, the total amount of (2)+(3) or (2)+(3)+(5) is at least 16 parts but less than 27 parts, better be about about 22 parts of 18-.
If use non-polymer additive such as graphitized carbon black, then they should add after functionalized polymeric and the reaction of maleic anhydride polymers grafted.Perhaps, separately prepare functionalized polymeric and the polyolefinic affixture of maleic anhydride grafted, then with the thermoplastic olefin blend.
Composition of the present invention also can comprise other conventional additive, for example oxidation inhibitor; Stablizer; Extending oil such as paraffin oil and naphthenic oil; Filler such as CaCO
3, talcum and zinc oxide, or fire retardant.
Can be in open roll, in internal mixer (Banbury or Haake mixing machine) and single screw rod or the twin-screw extruder each component of composition is mixed or melt blending.
Randomly in advance blend maleic anhydride polymers grafted or with the thermoplastic olefin blend before they can with component (4) pre-reaction.Yet preceding a kind of method is better.
In following embodiment and Comparative Examples, under 450 temperature, in twin-screw extruder, do each component of blend and reaction mixing, the material granulation to gained prepares the used sample of test then.Pellet is injection molded into dish, uses Du Pont 872 white paint that this dish is applied, make its coating, solidified 30 minutes down at 250 °F with about 1.2-2 mil thick.With the dish through applying of the opposite side of gate area of dish on the tartan design of delineation grid, the size of each grid is about 1/4 inch.Adhesive tape (3M 898) is pressed onto paint goes up and shut down, to test amount of paint or the paint adhesion of being removed.To pull once the % number scale record destructive % number of the grid of being removed by adhesive tape the back.Use the Taber abrader to measure wearing quality with a C type wearing and tearing subassembly (scuffing headassembly) and 1 pound of load.Will dish be placed in 70 ℃ the baking oven 1 hour, take out, be placed on the platform of abrader through applying.Wearing and tearing heads is contacted with the surface that applied, allow the specified cycle number of disc spins.To be designated as from the amount of paint that the full circumferences that faces toward with the wearing and tearing head is removed and destroy %.
One group of standard of acceptable paint adhesion be by adhesive tape record destruction (coating of being removed) less than 10% and the paint removed 25 circulation backs with the Taber abrader for less than 20%, the paint of being removed 50 circulation backs is 30% or still less.
In this manual, except as otherwise noted outside, all umbers and percentage number average are by weight.
Embodiment 1-7
Embodiment 1-7 explanation comprises thermoplastic olefin (TPO), the maleic anhydride grafted olefin polymer material (MA-g-OPM) of various amounts, maleic anhydride grafted polypropylene (MA-g-PP) and the end capped polyethylene oxide of amine (ATPEO) contain or do not contain the paint adhesion and the wearing quality of the composition of maleic anhydride grafted polyethylene (MA-g-PE).The results are shown in Table 1.
In this table, thermoplastic olefin comprises 55% alfon, 3% propylene content is about 10% and at room temperature be insoluble to the semi-crystalline ethylene/propylene copolymer of dimethylbenzene, 30% ethylene content is 50% and at room temperature is dissolved in the amorphous ethylene/propylene copolymer rubbers of dimethylbenzene and the Alathon that 12% melt index is about 50g/10min.
MA grafted OPM (1) is the Exxelor VA-1803 ethylene/propylene rubber that contains 0.7% grafting maleic anhydride available from Exxon Chemial Company.
MA grafted OPM (2) is the 0.4% grafting maleic anhydride that comprises available from Uniroyal Chemical Co.Inc., mooney viscosity (ML 1+4 in the time of 125 ℃) be 60 and the ratio of ethylene/propene be the terpolymer of Royaltuf465A ethylene/propene/non-conjugated diene of 75/25.
MA grafted polypropylene is the maleic anhydride-modified Poly Propylene Wax of Epolene E-43 available from Eastman Chemical Company.
MA grafted polyethylene is the Ceramer 67 maleic anhydride grafted polyethylene waxs available from Petrolite Corporation.
ATPEO is the end capped polyethylene oxide of XTJ-418 monoamine available from Huntsman Corporation.
Oxidation inhibitor is the Irganox B 225 available from Ciba-Geigy, it is 1 part of Irganox 1,010 2,2-is two, and [[3-(3,5-two (1, the 1-dimethyl ethyl)-the 4-hydroxy phenyl]-the 1-oxopropoxy) methyl]-1,3-glyceryl-3,5-two (1, the 1-dimethyl ethyl)-mixture of 4-hydroxy phenylpropionic acid ester stabilizer and 1 part of Irgasfos 168 tricresyl phosphite (2, the 4-di-tert-butyl-phenyl) ester.
| Table 1 | |||||||
| Embodiment 1 | Embodiment 2 | Embodiment 3 | Embodiment 4 | Embodiment 5 | Embodiment 6 | Embodiment 7 | |
| ?TPO | ????100 | ????100 | ????100 | ????100 | ????100 | ????100 | ????100 |
| ?MA-g-OPM(1) | ????5 | ?????5 | ????10 | ????10 | ????5 | ????10 | ????10 |
| ?MA-g-OPM(2) | ????5 | ?????5 | ????- | ????- | ????- | ????- | ????- |
| ?MA-g-PP | ????10 | ????10 | ????10 | ????10 | ????10 | ????10 | ????10 |
| ?MA-g-PE | ????- | ????5 | ????- | ????- | ????10 | ????- | ????- |
| ?ATPEO | ????3 | ????3 | ????3 | ????4 | ????3 | ????3 | ????4 |
| Oxidation inhibitor | ????0.2 | ????0.2 | ????0.2 | ????0.2 | ????0.2 | ????0.2 | ????0.2 |
| Paint adhesion destroys % | ????3 | ????0 | ????6 | ????0 | ????0 | ????9 | ????0 |
| Wearing quality is destroyed % | |||||||
| 25 circulations | ????10 | ????0 | ????8 | ????15 | ????0 | ????15 | ????15 |
| 50 circulations | ????20 | ????0 | ????8 | ????20 | ????12 | ????15 | ????25 |
Embodiment 1,3, and 4,6 and 7 show that the mixture of MA grafted polypropylene and MA grafted ethylene/propene olefin polymer material can obtain good binding property and wearing quality.Embodiment 2 and 5 shows MA grafted polyethylene and MA grafted polypropylene and MA grafted olefin polymer material mixing energy are obtained improvement slightly and improve wearing quality on paint adhesion.
Comparative Examples 1-4
In table 2, Comparative Examples 1 used not graft rubber is the ter-polymer rubber available from the Dutral that comprises 4% ethylidene norbornene 4038 ethylene/propylene/ethylidene norbornenes of Enichem America Inc..The prescription other all components all with embodiment 1-7 in identical.
| Table 2 | ||||
| Comparative Examples 1 | Comparative Examples 2 | Comparative Examples 3 | Comparative Examples 4 | |
| ????TPO | ????100 | ????100 | ????100 | ????100 |
| Rubber | ????10 | ?????- | ????- | ????- |
| ????MA-g-OPM(1) | ????- | ?????- | ????5 | ????- |
| ????MA-g-OPM(2) | ????- | ?????- | ????5 | ????- |
| ????MA-g-PP | ????10 | ????20 | ????5 | ????10 |
| ????MA-g-PE | ????- | ????- | ????10 | ????10 |
| ????ATPEO | ????4 | ????4 | ????3 | ????3 |
| Oxidation inhibitor | ????0.2 | ????0.2 | ????0.2 | ????0.2 |
| Paint adhesion destroys % | ????45 | ????0 | ????54 | ????28 |
| Wearing quality is destroyed % | ||||
| 25 circulations | ????28 | ????45 | ????28 | ????0 |
| 50 circulations | ????44 | ????55 | ????50 | ????1 |
Comparative Examples 1 shows that adding does not obtain the binding property of difference and the wearing quality of difference with maleic anhydride grafted rubber.Comparative Examples 2 shows the MA grafted polypropylene that adds more amount but does not add the good binding property of MA grafted OPM acquisition, but wearing quality remains poor.Comparative Examples 3 shows mixes binding property and the poor wearing quality that obtains difference with a small amount of MA grafted polypropylene (5 parts) with MA grafted OPM.Comparative Examples 4 shows mixes MA grafted polypropylene and does not add MA grafted olefin polymer material and obtain good wearing quality with MA grafted polyethylene, but paint adhesion is poor.
Embodiment 8-11
Embodiment 8-11 shows and comprises thermoplastic olefin (TPO), maleic anhydride grafted olefin polymer material (MA-g-OPM), the functionalized polymeric of maleic anhydride grafted polypropylene (MA-g-PP) and three types, be the end capped polyethylene oxide of amine (ATPEO), the paint adhesion and the wearing quality of the composition of hydroxylated polyethylene (HPE) and hydroxylated polybutene (HPB).The results are shown in Table 3.
In table 3, thermoplastic elastomer, maleic anhydride grafted olefin polymer material (1) and (2), identical in the maleic anhydride grafted polypropylene, the end capped polyethylene oxide of amine and oxidation inhibitor and embodiment 1-7.
Maleic anhydride grafted OPM (3) is that to comprise (a) 30% ethylene content be 3.3% propylene-ethylene random copolymer, (b) the 6.8% semi-crystalline ethylene/propylene copolymer component that at room temperature is insoluble to dimethylbenzene, (c) 63.2% amphoteric polymeric material that at room temperature is dissolved in the amorphous ethylene/propene copolymer component of dimethylbenzene, maleic anhydride grafted OPM (3) also comprises 1% grafted maleic anhydride.
MA-g-PE is the Ceramer 67 maleic anhydride grafted polyethylene waxs available from Petrolite Corporation.
HPE is the Unilin 350 hydroxylated polyethylene waxs available from Petrolite Corporation.
HPB is the HPVM 2202 hydroxylated polybutene available from Shell Chemical Company.
| Table 3 | ||||
| Embodiment 8 | Embodiment 9 | Embodiment 10 | Embodiment 11 | |
| ????TPO | ????100 | ????100 | ????100 | ????100 |
| ????MA-g-OPM(1) | ????- | ????- | ????- | ????5 |
| ????MA-g-OPM(2) | ????- | ????10 | ????10 | ????- |
| ????MA-g-OPM(3) | ????10 | ????- | ????- | ????- |
| ????MA-g-PP | ????10 | ????10 | ????10 | ????10 |
| ????MA-g-PE | ????- | ????- | ????- | ????10 |
| ????ATPEO | ????3 | ????- | ????- | ????- |
| ????HPE | ????- | ????6 | ????- | ????- |
| ????HPB | ????- | ????- | ????3 | ????3 |
| Oxidation inhibitor | ????0.2 | ????0.2 | ????0.2 | ????0.2 |
| Paint adhesion destroys % | ????0 | ????0 | ????0 | ????0 |
| Wearing quality is destroyed % | ||||
| 25 circulations | ????0 | ????18 | ????13 | ????0 |
| 50 circulations | ????0 | ????26 | ????18 | ????0 |
Comparative Examples 5-9
In table 4, thermoplastic olefin, maleic anhydride grafted olefin polymer material (1) and (3), identical in the maleic anhydride grafted polypropylene, the end capped polyethylene oxide of amine and oxidation inhibitor and embodiment 8-13.Except comprising 3% rather than 1% grafting maleic anhydride, maleic anhydride grafted OPM (4) is identical with maleic anhydride grafted OPM (3).
| Table 4 | |||||
| Comparative Examples 5 | Comparative Examples 6 | Comparative Examples 7 | Comparative Examples 8 | Comparative Examples 9 | |
| ?TPO | ????100 | ????100 | ????100 | ????100 | ????100 |
| ?MA-g-OPM(1) | ????- | ????10 | ????10 | ????- | ????- |
| ?MA-g-OPM(3) | ????- | ????- | ????- | ????10 | ????- |
| ?MA-g-OPM(4) | ????10 | ????- | ????- | ????- | ????10 |
| ?MA-g-PP | ????10 | ????10 | ????10 | ????- | ????- |
| ?ATPEO | ????3 | ????2.5 | ????7 | ????3 | ????3 |
| Oxidation inhibitor | ????0.2 | ????0.2 | ????0.2 | ????0.2 | ????0.2 |
| Paint adhesion destroys % | ????30 | ????18 | ????30 | ????100 | ????100 |
| Wearing quality is destroyed % | |||||
| 25 circulations | ????45 | ????35 | ????50 | ????100 | ????100 |
| 50 circulations | ????55 | ????38 | ????75 | ????100 | ????100 |
These Comparative Examples show as MA-g-OPM and comprise 3% or more grafting maleic anhydride (Comparative Examples 5 and 9), use too much or during ATPEO very little (Comparative Examples 6 and 7) and when not comprising MA-g-PP (Comparative Examples 8 and 9) in composition, binding property and wearing quality all are unacceptable.
Embodiment 12 and 13
These embodiment illustrate use end capped polyalkylene glycol of amine and hydroxylation mixture of polymers as functionalized polymeric, i.e. the component of the present composition (4).The results are shown in Table 5.
In table 5, thermoplastic olefin, maleic anhydride grafted polypropylene, maleic anhydride grafted olefin polymer material (1) and (2), used identical among ATPEO and oxidation inhibitor and the embodiment 1-7.Used identical among HPE and HPB and the embodiment 8-11.
| Table 5 | ||
| Embodiment 12 | Embodiment 13 | |
| ????TPO | ????100 | ????100 |
| ????MA-g-OPM(1) | ????5 | ????5 |
| ????MA-g-OPM(2) | ????5 | ????5 |
| ????MA-g-PP | ????10 | ????10 |
| ????ATPEO | ????3 | ????3 |
| ????HPE | ????3 | ????- |
| ????HPB | ????- | ????1 |
| Oxidation inhibitor | ????0.2 | ????0.2 |
| Paint adhesion destroys % | ????0 | ????0 |
| Wearing quality is destroyed % | ||
| 25 circulations | ????8 | ????16 |
| 50 circulations | ????20 | ????28 |
The further feature of present invention disclosed herein, advantage and embodiment will be very conspicuous after having read foregoing concerning those those of ordinary skills.Therefore, though described in detail specific embodiments of the present invention, the changes and improvements of these embodiments all can realize under the situation of the spirit and scope of the present invention that do not depart from said and requirement.
Claims (8)
1. composition, it comprises by weight:
(1) 100 part of thermoplastic olefin that comprises following (a)-(d):
(a) about 60% isotactic index of about 10%-is greater than 90% alfon, or propylene content greater than 85% and isotactic index greater than 85% comprise ethene and/or C
4-8The crystalline propylene copolymer of alpha-olefin;
(b) about 30%-about 60% randomly comprises the amorphous ethylene-propylene or the ethylene-butene copolymer component of about 10% diene of about 1%-, and described copolymer component at room temperature is dissolved in dimethylbenzene and comprises the ethene of about 30%-about 70%;
(c) be insoluble to dimethylbenzene under about 20% room temperature of about 2%-and comprise greater than 75% but less than the semi-crystalline ethylene-propylene or the ethylene-butene copolymer of 92% ethene; With
(d) about 20% density of about 5%-is 0.91-0.96/cm
3, melt index is the ethene polymers of 0.1-100g/10min;
(2) to be about 2%-about 5% for about 8 parts-Yue 14 parts of maleic anhydride content of per 100 parts of thermoplastic olefins, molecular weight M
nThe maleic anhydride grafted alfon or the ethylene/propylene olefinic random copolymer that are about 2500-about 25,000;
(3) 14 parts of about 5 parts of per 100 parts of thermoplastic olefins-Yue maleic anhydride content of being selected from following (a)-(b) is at least 0.3% but less than 3% maleic anhydride grafted olefin polymer material:
(a) comprise ethylene/propene or ethylene/butylene copolymers rubber, randomly comprise the maleic anhydride grafted polyolerin elastomer of about 10% diene of about 0.5%-, described copolymer rubber comprise about 30%-about 70% ethene and
(b) maleic anhydride grafted amphoteric polymeric material, wherein amphoteric polymeric material mainly comprises following component (ⅰ)-(ⅲ):
(ⅰ) about 50% isotactic index of about 10%-is about the alfon of 80%-about 99%, or is selected from the multipolymer of following (a)-(c), (a) propylene and ethene, (b) propylene, ethene and CH
2=CHR alpha-olefin, wherein R is C
2-8The straight or branched alkyl and (c) propylene and as above-mentioned (ⅰ) (b) in defined alpha-olefin, this multipolymer comprises the propylene of about 85%-about 99%, and isotactic index is about 80%-about 98%;
(ⅱ) about 3%-about 20% records the copolymer component that degree of crystallinity is about the hemicrystalline line style basically of 20%-about 60% by dsc (DSC), and wherein multipolymer is selected from following (a)-(c), (a) contains ethene and propylene greater than 50% ethene; (b) contain about 10% alpha-olefin of about 1%-and greater than the ethene of 50% to 98% ethene and alpha-olefin, propylene and as above-mentioned (ⅰ) (b) in defined alpha-olefin; (c) contain greater than the ethene of 50% to 98% alpha-olefin and as above-mentioned (ⅰ) (b) in defined alpha-olefin, described multipolymer is insoluble to dimethylbenzene under room temperature or envrionment temperature; With
(ⅲ) about 40%-about 80% is selected from the copolymer component of following (a)-(c) multipolymer, (a) ethene and propylene, and wherein multipolymer contains 20%-less than 40% ethene; (b) ethene, propylene and as above-mentioned (ⅰ) (b) in defined alpha-olefin, wherein to be about 1%-about 10% for the amount of alpha-olefin, the amount of ethene and alpha-olefin is that 20%-is less than 45%; (c) comprise 20%-less than 45% alpha-olefin and randomly comprise about 10% diene of about 0.5%-ethene and as above-mentioned (ⅰ) (b) defined alpha-olefin, copolymer component (ⅲ) is dissolved in dimethylbenzene at ambient temperature, its limiting viscosity is about about 3.0 dl/g of 1.7-, wherein in the total amount of olefin polymer compositions, component (ⅱ) and total amount (ⅲ) are about 65%-about 80%, it is about 0.3 that the weight ratio of component (ⅱ)/(ⅲ) is about 0.1-, ethene or C in component (ⅱ)+(ⅲ)
4-8The total content of alpha-olefin or their mixture is less than 50%; With
(4) be selected from following (a)-(c), and the functionalized polymeric of acid anhydride radical reaction in the graftomer:
(a) the about 6 parts of end capped polyalkylene glycols of amine of per 100 parts of about 2.7-of thermoplastic olefin;
(b) the about 6 parts of hydroxylation polymkeric substance that are selected from following (ⅰ)-(ⅲ) of per 100 parts of about 2-of thermoplastic olefin:
(ⅰ) hydroxylation polyethylene,
(ⅱ) the hydroxylation polybutene and
(ⅲ) hydroxylated polybutadiene; With
(c) mixture of per 100 parts of about 2-of thermoplastic olefin about 6 parts (a)+(b), wherein to be about 0.1-about 0.9 for (a) and (b) ratio,
In wherein per 100 parts of thermoplastic olefins, (2)+(3) are at least 16 parts but less than 27 parts.
2. composition as claimed in claim 1 is characterized in that (4) are the end capped polyalkylene glycols of amine.
3. composition as claimed in claim 1 is characterized in that (4) are (a) and mixture (b), and in per 100 parts of thermoplastic olefins, total amount (a)+(b) is about about 6 parts of 2-, (a) is about 0.1-about 0.9 with (b) ratio.
4. composition as claimed in claim 1, it also comprises (5), and about 4 parts-Yue 15 parts of maleic anhydride content of per 100 parts of thermoplastic olefins are about 2%-about 13% and molecular weight M
nThe maleic anhydride grafted ethene polymers that is about 500-about 3000, (2)+(3)+(5) are at least 16 parts but less than 27 parts in wherein per 100 parts of thermoplastic olefins, and (3)+(5) are equal to or greater than 10 parts in per 100 parts of thermoplastic olefins.
5. composition as claimed in claim 4 is characterized in that (4) are the end capped polyalkylene glycols of amine.
6. composition as claimed in claim 4 is characterized in that (4) are (a) and mixture (b), and in per 100 parts of thermoplastic olefins, total amount (a)+(b) is about about 6 parts of 2-, (a) is about 0.1-about 0.9 with (b) ratio.
7. injection-molded item, it comprises composition as claimed in claim 1.
8. injection-molded item, it comprises composition as claimed in claim 4.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 98103858 CN1225935A (en) | 1998-02-13 | 1998-02-13 | Thermoplastic olefin compositions containing maleic anhydride-modified polymers and capable of directly painting |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 98103858 CN1225935A (en) | 1998-02-13 | 1998-02-13 | Thermoplastic olefin compositions containing maleic anhydride-modified polymers and capable of directly painting |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN1225935A true CN1225935A (en) | 1999-08-18 |
Family
ID=5218085
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN 98103858 Pending CN1225935A (en) | 1998-02-13 | 1998-02-13 | Thermoplastic olefin compositions containing maleic anhydride-modified polymers and capable of directly painting |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN1225935A (en) |
-
1998
- 1998-02-13 CN CN 98103858 patent/CN1225935A/en active Pending
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