CN1109706C

CN1109706C - Polyethex amine modification of polypropylene

Info

Publication number: CN1109706C
Application number: CN96195344A
Authority: CN
Inventors: R·K·埃文斯; R·J·G·多明格兹; R·J·克拉克
Original assignee: Huntsman Petrochemical LLC
Current assignee: Huntsman Petrochemical LLC
Priority date: 1993-07-13
Filing date: 1996-07-08
Publication date: 2003-05-28
Anticipated expiration: 2016-07-08
Also published as: CN1190413A

Abstract

This invention concerns a composition comprising a blend of polyolefin with the reaction of a functionalized polyolefin and polyetheramine in which the polyetheramine is grafted into the functionalized polyolefin in a customary mixing apparatus. The blend may include an elastomer such as EP rubber and/or a filler such as glass. A process for producing the reaction product of functionalized polypropylene and polyetheramine by melting with polypropylene in a customary mixing apparatus is also disclosed. Blends of the present invention are advantageously useful to prepare paintable automotive body parts. A polyether monoamine that contains from about 36 to about 44 ethylene units and from about 1 to about 6 propylene units, and processes and blends using same.

Description

Polyacrylic polyethex amine modification

The present invention relates to a kind of novel olefin polymer, it comprises the reaction product of functionalization polypropylene and polyetheramine.The invention still further relates to and contain this new olefine polymerization thing and polyacrylic thermoplastic resin composition.The invention still further relates to polyetheramine.

The method of compatilizer that forms alloyed polymer on the spot is popular just rapidly.Recent years, the example that the advantage of utilizing reactive group to exist forms grafting or block or random copolymers gets more and more, and this multipolymer can be used as the compatilizer of two or more polymeric blends.Prior art, S.S.Dagli, the processing requirement of the reactive compatibilization of nylon 6/ polypropylene blend of M.Xanthos and J.A.Biensenberger ( Process Requirements of the Reactive Compatibilization of Nylon6/Polypropylene Blends): PolymerProcessing Institute, Stevens Institute of Technology, Hoboken, N.J.07030 have illustrated the acrylic graft-modified polypropylene that uses with nylon-6 and polyacrylic blend.

Containing polyacrylic thermoplastic resin composition is that the crowd knows in this area in (as United States Patent (USP) 5,208,081).United States Patent (USP) 5,179,164 have described a kind of polypropylene/daiamid composition that is suitable for preparing moulded product.This patent has been described a kind of can be used as and has been increased attached dose ethylene copolymer.In addition, this patent shows that toxilic acid is the suitable monomer of this ethylene copolymer of preparation.

And maleation polypropylene can have been bought on market.

European patent application 0 367 832 discloses a kind of resin combination that contains the olefin polymer that has anhydride group.As at United States Patent (USP) 5,179, the same in 164, the mixing material that this is novel and polyamide blended.

Japanese Patent 46003838 discloses a kind of maleic anhydride modified polypropene composition, and it contains triethylamine and polyethylene glycol nonylphenyl ether.Japanese Patent 60195120 discloses a kind of polyethylene of polyethylene, maleic anhydride graft and moulded product of diethylenetriamine of containing.

Yet the present invention is used in combination maleic anhydride with polyetheramine, and the performance of resin is had beyond thought raising.

The present invention relates to a kind of mixing material, this mixing material comprises the blend of the reaction product of polypropylene (" PP ") and functionalization polypropylene and polyetheramine, and wherein this polyetheramine is grafted on the functionalization polypropylene in mixing device commonly used.Grafting is meant the amine functionality of polyetheramine and the acid anhydrides component reaction of functionalization polypropylene, forms reaction product, and for example the reaction of primary amine and maleic anhydride forms imide.The invention still further relates to a kind of by in mixing device commonly used, preparing the method for the reaction product of functionalization polypropylene and polyetheramine with polypropylene fusion.In this respect, blend of the present invention can be by carrying out reactivity and extrude and prepare the reaction of polyetheramine and functionalization polypropylene being formed under the temperature of the reaction product contain imide group polyetheramine, functionalization polypropylene and polypropylene be added in the forcing machine.

The invention still further relates to the polyether monoamine that contains have an appointment 36～about 44 ethylene oxide units and about 1～about 6 propylene oxide units.Ethylene oxide unit and propylene oxide unit refer to the residual structure after ethylene oxide and propylene oxide mix in the polyether monoamine, promptly correspond respectively to-CH ₂CH ₂O-and-CH ₂CHCH ₃The unit of O-.The invention still further relates to a kind of preparation and contain the method for the blend of polypropylene and functionalization polypropylene and polyether monoamine reaction product, this method forms blend by melt polypropylene, polyether monoamine and functionalization polypropylene and carries out.The invention still further relates to the blend that contains polypropylene and polyether monoamine and functionalization polypropylene reaction product.

Composition of the present invention can be used for preparing molded car body component, comprises the basic car body component of TPO (" TPO ") that directly can spray.

In addition, composition of the present invention also can be used for preparing the mo(u)lded item that contains filler such as glass.Composition of the present invention also can be used for preparing film, but comprises print film; Fiber comprises and can dye and the nonwoven polypropylene fiber; And as the wrapping material of electronic components such as semi-conductor chip, wherein wrapping material make electrostatic dissipation and prevent that chip from damaging.Composition of the present invention also can be used for improving poly barrier performance and the modification polyethylene as tack coat in multilayer film article.Composition of the present invention also can be used as the additive of the polypropylene-base fortifying fibre that is used for cement.

Polypropylene of the present invention is compared with the blend of maleation polypropylene with polypropylene with the blend of the reaction product of polyetheramine with maleation polypropylene, and coating character is improved, and shock-resistance has had raising, and mold flow properties is fine.

Plastics are used for the production of motor vehicle more and more.Verified, impact modified polypropylene is particularly suitable for some application, as safety lever, spolier, backplate and roadside buffer strip (sidebump strips) or the like.Therefore, the present invention has the thermoplastic resin composition that improves performance very tangible potential commercial value is arranged.

These resin combinations according to the present invention can be used as engineering plastics, and this project plastics are the materials that are used for structural element and junctor, pipe etc. in fields such as transportation machine (automobile, steamer etc.), instrument, instrument, electronic apparatus, electric appliance, sports equipment, leisure goods.

In polymer chemistry, suitable polypropylene is well-known, as at R.Vieweg, the Kunststoff-Handbuch that A.Schley and A.Schwarz edit, IV volume, Polyolefins, Carol Hanser Verlag, Munich has explanation in 1969, and can buy on the market, therefore no longer describe in detail.

Functionalization polypropylene for grafting on it monomeric polypropylene.Common grafting method is to pass through free radical reaction.In enforcement of the present invention, maleation polypropylene is not the multipolymer of maleic anhydride or its Equivalent and propylene, because like this, the maleic anhydride part mainly is arranged in the skeleton of this multipolymer.The suitable monomer of preparation functionalization polypropylene has carbonatoms for example to be less than 12 olefinic unsaturated monocarboxylic such as acrylic or methacrylic acid and the corresponding tert-butyl ester thereof as (methyl) tert-butyl acrylate; Carbonatoms is less than the list or the di tert butyl carbonate of the list of 12 olefinic unsaturated dicarboxylic acid such as fumaric acid, toxilic acid, methylene-succinic acid and corresponding list and/or di tert butyl carbonate such as fumaric acid or di tert butyl carbonate, toxilic acid; Carbonatoms is less than the acid anhydrides such as the maleic anhydride of 12 olefinic unsaturated dicarboxylic acid; Carbonatoms is less than 12 the ethylenically unsaturated monomer that contains sulfo group or alkylsulfonyl such as right-styrene sulfonic acid, 2-(methyl) acrylamide-2-methacrylic sulfonic acid or 2-alkylsulfonyl (methyl) acrylate; Carbonatoms is less than ethylenically unsaturated monomer such as the Yi Xi oxazolin and the Yi Xi oxazolin derivs of 12 Han You oxazolinyl; And carbonatoms is less than 12 the ethylenically unsaturated monomer that contains epoxy group(ing) as (methyl) glycidyl acrylate or glycidyl allyl ether.The most preferred monomer of preparation functionalization polypropylene is a maleic anhydride.

The number-average molecular weight variation range that is used for functionalization polypropylene of the invention process is wide.When functionalization polypropylene was used to prepare the workpiece that can spray such as car body component, it is about 3,000 that the number-average molecular weight of functionalization polypropylene is preferably greater than, and preferably less than about 20,000, be more preferably less than about 10,000.The present EPOLENE E-43 of a typical example of the maleation polypropylene of listing for having bought from Eastman Chemical.According to enforcement of the present invention, after the functionalization polypropylene of this class lower molecular weight and the polyetheramine reaction, make the easier coating of extrusion compositions of gained.Use in the application of functionalization polypropylene at other, as when adding glass filler when improving stiffness and intensity, use is greater than 40,000 and be lower than 60,000 higher number average molecular weight.Generally speaking, glass filler and polypropylene are immiscible, and their combination produces the space usually in the composition of gained.Material " humidifying " glass that molecular weight is higher makes the easier combination of glass filler particle and polypropylene, thereby reduces the pore volume in the resulting composition.

Suitable anhydride functional polypropylene comprises following structure: Or Wherein PP is a polypropylene.Should be appreciated that in these structures, when polypropylene when being linear, polypropylene can with one or two monomer bonding; And when polypropylene was branching, it can comprise greater than two monomers.In typical case, there is one or two monomer.

Suitable polyetheramine comprises monoamine, and its molecular weight is 150 to 12,000.The molecular weight of preferred, polyethers amine is 1,000 to 3,000.Comprise JEFFAMINE M-1000, JEFFAMINE M-2070 and JEFFAMINE M-2005 at the suitable monoamine shown in the glossary.Preferred polyetheramine is JEFFAMINE M-2070.The molecular weight of preferred polyetheramine of the present invention is in 1500 to 2000 scopes.The suitable polyether block of polyetheramine comprises the multipolymer of polyoxyethylene glycol, polypropylene glycol, polyoxyethylene glycol and polypropylene glycol, poly-(1, the 2-butyleneglycol) and poly-(1, the 4-butyleneglycol).The method that available crowd knows makes polyetheramine with these glycol aminations.Generally speaking, prepare these glycol as the reaction that causes by methoxyl group or hydroxyl by ethylene oxide, propylene oxide or their mixture with many methods of knowing.When use ethylene oxide and propylene oxide the two the time, atactic polyether if desired, these oxide compounds can react simultaneously; Block polyether if desired, they can carry out consecutive reaction.

Particularly preferred polyetheramine is a polyether monoamine, and it contains 36～44 ethylene oxide units and 1～6 propylene oxide unit.In one embodiment, the molecular weight of such polyether monoamine is 2000 to 2200.In another embodiment, polyether monoamine comprises 40～43 ethylene oxide units and 2.4～6, preferred 2.4～3 propylene oxide units.The structure of some polyether monoamines is as follows:

Wherein m is 36～44, and n is 1～6, it comprise m wherein be 40～43 and n be 2.4～3 polyether monoamine, and molecular weight is 2000～2200 following formula compound.

In one embodiment of the invention, prepare polyetheramine with ethylene oxide, propylene oxide or their mixture.Generally speaking, when preparing polyetheramine with ethylene oxide, propylene oxide or their mixture, the mole number of ethylene oxide is preferably greater than 75%, more preferably greater than 90% greater than 50% of polyetheramine.In one embodiment of the invention, polyvalent alcohol and comprise polyalkylene polyamine and alkanolamine or any be not that the amine of the amine of polyetheramine disclosed by the invention can be in said composition.Equally, polyetheramine can not have ehter bond and amido functional group in addition.Being used for polyetheramine of the invention process can know amination method preparation with the crowd, as at United States Patent (USP) 3,654, and 370, United States Patent (USP) 4,152,353, United States Patent (USP) 4,618, and 717, United States Patent (USP) 4,766,245, United States Patent (USP) 4,960, and 942, United States Patent (USP) 4,973,761, United States Patent (USP) 5,003, and 107, United States Patent (USP) 5,352,835, United States Patent (USP) 5,422,04 and United States Patent (USP) 5,457,147 in illustrated.Usually, by at catalyzer such as nickel-containing catalyst, as the Ni/Cu/Cr catalyzer exist down with ammonia will many alcohol amination prepares polyetheramine as polyether polyol.

Functionalization polypropylene and polyetheramine and dispensable polyacrylic mixing can be carried out in mixing device commonly used, and this device comprises batch mixer, continuous mixer, kneader and forcing machine.Use for majority, preferred mixing device is a forcing machine.

In order to improve shock strength, this resin combination also contains the elastomerics of impact modifying agent, particularly impact-modified performance except containing polypropylene/functionalization polypropylene of the present invention/polyetheramine structural group especially.For the skilled work personnel, the elastomerics that is used for impact-modified performance of the present invention is that the crowd knows.For example having with ethene, propylene, divinyl and acrylate such as methacrylic ester or their mixture is the rubber of base.Other example comprises EP and EPDM rubber, and EP rubber (ethylene propylene rubber) is preferred for preparing in the application of car body component.The VISTALON 878 that a typical example of at present commercially available EP rubber is Exxon Chemical.

The elastomerics of suitable impact-modified performance for example in organic chemistry method (Methoden derorganischen Chemie) (Houben-Weyl), the XIV/1 volume, MakromolekulareChemie (Georg-Thieme-Verlag, Stuttgart, 1961), the monograph of p390～406 and C.B.Bucknal is illustrated in " toughened plastics (Toughened Plastics) " (AppliedPublishers, London, 1977).

The composition that contains polypropylene and elastomerics such as EP rubber often is called " TPO ", and it represents TPO.TPO is usually used in preparing the car body component of molding, for example bumper beam (bumper fascias).Such molded parts also can comprise following other component such as filler.With TPO is the composition that basic preparation of compositions mode contains inelastic body together.TPO usually sells in the mode of compounding or reactor grade (reactor grade).The typical example of commercially available TPO describes in the following paragraph of embodiment 1-4 front in the market.

Estimate that polyetheramine and functionalization polypropylene and dispensable a spot of polypropylene or TPO can react, form the reaction product enriched material, then this reaction product enriched material can with polypropylene or TPO blend.In this one side of the present invention, polyetheramine accounts for the 10wt.%～50wt.% of this enriched material.When the reaction product of polyetheramine and maleation polypropylene prepares with respective pure form, other component blend or the compounding of this reaction product and polypropylene or TPO and desired composition can be arrived desired content with mixing device such as forcing machine.Be to be understood that polypropylene is usually used in the diluting reaction product.According to the kind of mixing machine, reaction product, polypropylene and any other component thoroughly mixed with the solid form before blend is incorporated into mixing device.Perhaps, can use the mixing machine that in operating process, mixes each component.Under above-mentioned arbitrary situation, in the operating process of mixing machine, the heating each component is with molten solids, and the mixed melting component forms final composition subsequently.

In resin combination of the present invention, except containing structural constituents such as polypropylene, functionalization polypropylene, polyetheramine and impact property properties-correcting agent, this resin also can contain toughener and/or additive.Used toughener can be reinforcing filler such as carbon or carbon fiber; Clay, chalk, talcum and the mica of control contraction and thermal expansivity; Improve the glass (pearl or fiber) of stiffness.And filler can be modified with increasing attached dose and/or sizing agent.Can add in addition as the phosphorous acid ester of stablizer (as free-radical scavengers) or hindered phenol or the two.

When composition comprises glass filler, the composition of high stiffness if desired, said composition can contain 40% glass filler at the most.More in typical case, the glass filler that uses in said composition is 2%～10%.Advantageously, the present invention contains the general space that does not produce usually basically of composition of glass filler in the composition that contains polypropylene and glass.Although be not wishing to be bound by theory, it is believed that the reaction product of polyetheramine and maleation polypropylene makes glass " humidifying ", glass and polypropylene are easier to combine (more miscible) thereby make.Of the present invention this on the one hand, preferably using above-mentioned molecular-weight average is 40,000～60,000 maleation polypropylene.

Preferred functionalization polypropylene is the maleation polypropylene with following structure: Wherein PP is a polypropylene.

Preferred polyetheramine is monoamine and diamines.The molecular weight of preferred monoamine and preferred triamine is 200～4000.The molecular weight of preferred diamines is 148～6000.The molecular weight of preferred monoamine and diamines is 1,000～3,000.

Preferred functionalization polypropylene is that the preferred reaction product between maleation polypropylene and the preferred polyetheramine has following formula: Wherein a is 5～50,000, and b: c is 0: 100～100: 0, and x is 1～3, and R is that hydrogen or functionality are the alkyl (even x is 2, and then R is a divalence) of x, and alkyl has 1～10 carbon atom.

Suitable thermoplastic resin composition can be contained 66wt%～80wt%, polypropylene, the maleation polypropylene of 20wt%～30wt% and the polyetheramine of 2wt%～10wt% of preferred 70wt%～80wt%.When composition comprises elastomerics, as what be used for preparing car body component is elastomerics in the composition of base with TPO, said composition generally comprises the maleation polypropylene of 5wt%～40wt%, the polyetheramine of 2wt%～10wt% and the polypropylene of 50wt%～93wt%, and these per-cents are based on the weight of these components in the said composition.Preferably include maleation polypropylene, the polyetheramine of 2wt%～8wt% and the polypropylene of 62wt%～83wt% that elastomer compositions contains 15wt%～30wt%.

Preferred commonly used mixing device is a forcing machine, in this forcing machine, is 175～300 ℃ and the residence time to be that polyetheramine is grafted on the maleation polypropylene in 25～300 seconds the process in temperature.For exemplary composition of the present invention, be higher than this temperature range, begin to degrade, and be lower than this scope, said composition generally can fusion.Polypropylene mixes the non-reacted component of blend for this.Preferred range is 190～260 ℃.

Moulded parts by preparation of compositions of the present invention generally can directly spray.The typical example that is used for the lacquer commonly used of this purpose comprises carbamate groups and melamine base lacquer.This class is coated with lacquer available method commonly used and is used.Composition advantageously of the present invention can directly be painted, and does not need to carry out pre-treatment and not essential without priming paint, though also can use priming paint with chlorine.

In an embodiment, with having nine barrel structures, three Werner﹠amp that mediate a district and an emptying district; The twin screw extruder of Pfleiderer 30mm (ZSK30) carries out continuous compounding, and charging is parallel feeding in proper order, and wherein all components are at same position charging (loading hopper of forcing machine).

The embodiment of following explanation essence of the present invention is not used for limiting the present invention.In these embodiments, maleic functionality is that stoichiometry is excessive with respect to the amount of amine functionality on the polyetheramine on the maleation polypropylene.

In following embodiment 1-2, modification TPO base (thermoplastic olefin base) composition (table 1A and table 2A) that comprises polyetheramine of the present invention, the physicals (table 1B and table 2B) of said composition and the adhesion of coatings performance (table 1C, 2C, 4A and 4B) of said composition have been shown.In the table that embodiment 1～4 is given, the meaning of following term indication is as follows:

" HIMONT CA53A " is the TPO of reactor grade, and it contains polypropylene (" PP ") and ethylene propylene rubber (" EP rubber "), obtains from Himont, and melt flow can be described as medium.

" phenol " hindered phenol stabilizer ETHANOX 330 for obtaining by Albemarle.

" EPOLENE E-43 " maleation polypropylene for obtaining from Eastman Chemical, recording the maleation degree with proton magnetic resonance (PMR) is about 4wt%.

" HIMONT LB150161 " is the TPO of the high reactor grade of melt flow.

" AMOCO 1016 " are polypropylene, and supplier Amoco Chemical points out that its melt flow rate (MFR) is about 5g/min in the time of 230 ℃.

" DEXFLEX D-161 " is the compounding TPO of polypropylene and EP rubber, supplier D ﹠amp; S Plastics International illustrates that its melt flow is medium.

" NICHIBAN " refers to the trade mark of the adhesive tape that obtains from a Japanese firm.

" STAMYLAN P " shock resistance EP multipolymer for obtaining from DSM, the ethene that contains 5-10% in the skeleton, it is about 4.7dg/min with the melt flow that 150 R1133 methods record when the 230 ℃/2.16Kg that supplier Dutch State Mines (" DSM ") reports it.

" KELTAN TP-0552-2 " is a kind of TPO, and it is about 6.5dg/min with the melt flow that ISO R1133 method records when the 230 ℃/2.16Kg that supplier DSM reports it.

" VISTALON 878 " EP rubber for buying from Exxon Chemical.

" W/IPA " refers to clean with Virahol before japanning, and " W/OIPA " refers to Virahol scouring of no use.

In embodiment 1-4, sample composition is injection molded into I type tensile bar, and it is used for bond test.Following program is used for these embodiment.

Manual mixing polypropylene, maleation polypropylene, polyetheramine and oxidation inhibitor, the preparation blend joins in the loading hopper then.The band heater of forcing machine is set at following distribution: 200 ℃, 220 ℃, 220 ℃, 220 ℃, 220 ℃, 220 ℃ land areas of feed throat.

Blend joins Werner ﹠amp; The feed throat of Pfleiderer ZSK30 twin screw extruder.The compounding product cools off in water-bath and company's grain.

Specimen is carried out injection moulding with 55 tons of injection moulding machines of ENGEL, and used condition is as follows:

The heating zone:

Nozzle Next-door neighbour's nozzle Intake zone Intake zone

199℃ 196℃ 196℃ 196℃

27 ℃ of die temperatures

The physical testing sample allowed under 24 ℃ and 50% relative humidity balance 48 hours.According to ASTM D638, use crossbeam speed to be 10cm/min, measurement stretches on the INSTRON frame.According to ASTM D 790, use crossbeam speed to be 1.25cm/min, measure flexural property.According to ASTM D 256, measure beam type (Izod) impact property.

Dynamic mechanical spectra (DMS) is carried out with RHEOMETRICS RDS-II.The injection moulding strip of 12mm * 50mm * 3mm is tested under 1Hz with the vertical torsion pattern.The typical strain that puts on the sample is 0.05%～0.2%.Measurement shows in the zone of being studied, and is insensitive to strain.Under nitrogen atmosphere, be heated to sample melted with the heating rate of 2 ℃/min from-120 ℃, measure its storage modulus and out-of-phase modulus and loss tangent (tandelta).Sample is to test after regulating 24 hours under 50% the environment 24 ℃ and relative humidity.

The four inches injection molded trays of white dual-component polyurethane automobile finish spraying that provide with RED SPOT PAINTS are provided in the bonding test of lacquer.This lacquer applies with high volume, low pressure BINKS spray gun.The dish that is sprayed was 80 ℃ of bakings 30 minutes.Sample is tested with the bonding test mode of grid/adhesive tape after regulating 24 hours, with multiple-piece scriber 100 grids of generation (about 2mm of each grid * 2mm) on dish.(Scotch Brand 2040 3M) is added on the grid, adhesive tape is torn it down from dish again with an adhesive tape then.The reflection of per-cent shown in the table is with the spraying number of squares of adhesive tape from staying after dish tears it down.

Embodiment 1

Table 1A

Sample	PP ¹	MAL-PP ²	Amine ³	EP rubber ⁴	Phenol
Sample	PP ¹	MAL-PP ²	Amine ³	EP rubber ⁴	Phenol	1	74.7％	5％	-	20％	0.3％
2	69.7％	10％	-	20％	0.3％	1	74.7％	5％	-	20％	0.3％
2	69.7％	10％	-	20％	0.3％	3	59.7％	15％	-	25％	0.3％
4	70.7％	5％	4％	20％	0.3％	3	59.7％	15％	-	25％	0.3％
4	70.7％	5％	4％	20％	0.3％	5	68.7％	5％	6％	20％	0.3％
6	66.7％	5％	8％	20％	0.3％	5	68.7％	5％	6％	20％	0.3％
6	66.7％	5％	8％	20％	0.3％	7	65.7％	10％	4％	20％	0.3％
8	63.7％	10％	6％	20％	0.3％	7	65.7％	10％	4％	20％	0.3％
8	63.7％	10％	6％	20％	0.3％	9	61.7％	10％	8％	20％	0.3％
10	55.7％	15％	4％	25％	0.3％	9	61.7％	10％	8％	20％	0.3％
10	55.7％	15％	4％	25％	0.3％	11	53.7％	15％	6％	25％	0.3％
12	51.7％	15％	8％	25％	0.3％	11	53.7％	15％	6％	25％	0.3％

¹AMOCO 1016

²EPOLENE E-43

³The polyether monoamine that contains 40 ethylene oxide units and 2.4 propylene oxide units generally has the structural formula shown in the JEFFAMINE  M-2070 in glossary, is called in Hountsman Corporation " XTJ-418 ".

⁴VISTALON 878

Table 1B

	1	2	3	4	5	6
	1	2	3	4	5	6	Modulus in flexure, MPa	1233	1218	1134	1197	1098	994
Yielding stress, MPa	35.1	35.2	31.7	33.0	30.9	28.6	Modulus in flexure, MPa	1233	1218	1134	1197	1098	994
Yielding stress, MPa	35.1	35.2	31.7	33.0	30.9	28.6	Tensile elongation, %	189	182	148	159	262	116
Tensile strength, MPa	23.7	23.6	21.3	22.0	20.3	18.4	Tensile elongation, %	189	182	148	159	262	116
Tensile strength, MPa	23.7	23.6	21.3	22.0	20.3	18.4	Young's modulus, MPa	642	648	612	618	580	527
Hardness, Shore D	64	65	63	65	63	62	Young's modulus, MPa	642	648	612	618	580	527
Hardness, Shore D	64	65	63	65	63	62	Breach Izod shock strength, J/m	128	82	100	282	451	470
-30℃，J/m	15.2	16.2	17.2	16.0	15.6	23.1	Breach Izod shock strength, J/m	128	82	100	282	451	470
-30℃，J/m	15.2	16.2	17.2	16.0	15.6	23.1	Non-notch Izod shock strength, J/m	1056	1237	1144	1091	969	981
Dart impact performance							Non-notch Izod shock strength, J/m	1056	1237	1144	1091	969	981
Dart impact performance							Maximum load, J/m	1915	1848	1728	1788	1753	1408
-30℃，J/m	3480	3496	3325	2495	2191	479	Maximum load, J/m	1915	1848	1728	1788	1753	1408
-30℃，J/m	3480	3496	3325	2495	2191	479	Total energy, J	27.0	25.2	22.2	22.9	22.5	14.2
-30℃，J	43.5	40.0	42.2	20.4	9.6	2.0	Total energy, J	27.0	25.2	22.2	22.9	22.5	14.2
-30℃，J	43.5	40.0	42.2	20.4	9.6	2.0	Ductility/5	5	5	5	5	5	5
-30℃/5	5	4	5	2	0	0	Ductility/5	5	5	5	5	5	5

Table 1B (continuing)

	7	8	9	10	11	12
	7	8	9	10	11	12	Modulus in flexure, MPa	1161	1029	970	976	922	910
Yielding stress, MPa	32.1	29.2	28.5	26.8	25.6	25.3	Modulus in flexure, MPa	1161	1029	970	976	922	910
Yielding stress, MPa	32.1	29.2	28.5	26.8	25.6	25.3	Tensile elongation, %	374	240	118	376	474	185
Tensile strength, MPa	20.5	18.9	18.3	17.7	16.0	17.0	Tensile elongation, %	374	240	118	376	474	185
Tensile strength, MPa	20.5	18.9	18.3	17.7	16.0	17.0	Young's modulus, MPa	570	552	521	505	469	486
Hardness, Shore D	64	61	60	61	60	60	Young's modulus, MPa	570	552	521	505	469	486
Hardness, Shore D	64	61	60	61	60	60	Breach Izod shock strength, J/m	366	383	315	391	425	341
-30℃，J/m	17.9	16.8	19.2	20.2	19.8	17.6	Breach Izod shock strength, J/m	366	383	315	391	425	341
-30℃，J/m	17.9	16.8	19.2	20.2	19.8	17.6	Non-notch Izod shock strength, J/m	893	781	854	857	799	827
Dart impact performance							Non-notch Izod shock strength, J/m	893	781	854	857	799	827
Dart impact performance							Maximum load, J/m	1787	1449	1046	1546	1252	995
-30℃，J/m	3079	588	542	1668	676	492	Maximum load, J/m	1787	1449	1046	1546	1252	995
-30℃，J/m	3079	588	542	1668	676	492	Total energy, J	23.5	14.8	10.2	18.4	13.2	10.0
-30℃，J	20.8	2.6	2.6	7.0	2.6	2.2	Total energy, J	23.5	14.8	10.2	18.4	13.2	10.0
-30℃，J	20.8	2.6	2.6	7.0	2.6	2.2	Ductility/5	5	5	5	5	5	5
-30℃/5	0	0	0	0	0	0	Ductility/5	5	5	5	5	5	5

Table 1C

The bonding test of grid

Sample disc	S1		S2	S1	S2
Sample disc	S1		S2	S1	S2	Adhesive tape	3M ¹		3M	NICHIBAN	NICHIBAN
Sample	W/O IPA		W/O IPA	W/O IPA	W/O IPA	Adhesive tape	3M ¹		3M	NICHIBAN	NICHIBAN
Sample	W/O IPA		W/O IPA	W/O IPA	W/O IPA	PP ²	0％			1％
1	8％	4％	1％	12％	49％	PP ²	0％			1％
1	8％	4％	1％	12％	49％	2	1％	2％	4％	39％	43％
3	87％	90％	91％	97％	100％	2	1％	2％	4％	39％	43％
3	87％	90％	91％	97％	100％	4	49％	53％	57％	87％	95％
5	98％	98％	97％	100％	100％	4	49％	53％	57％	87％	95％
5	98％	98％	97％	100％	100％	6	99％	100％	100％	100％	100％
7	100％	100％	99％	100％	100％	6	99％	100％	100％	100％	100％
7	100％	100％	99％	100％	100％	8	98％	99％	100％	100％	100％
9	100％	100％	100％	100％	100％	8	98％	99％	100％	100％	100％
9	100％	100％	100％	100％	100％	10	100％		100％	100％	100％
11	100％		100％	100％	100％	10	100％		100％	100％	100％
11	100％		100％	100％	100％	12	100％		100％	100％	100％

¹Scotch Brand 2040

²Contrast

Embodiment 2

Table 2A

Sample	TPO ¹	MAL-PP ²	Amine ³	Phenol	PP ⁴
Sample	TPO ¹	MAL-PP ²	Amine ³	Phenol	PP ⁴	1	99.7％	-	-	0.3％
2	84.7％	-	-	0.3％	15％	1	99.7％	-	-	0.3％
2	84.7％	-	-	0.3％	15％	3	79.7％	-	-	0.3％	20％
4	89.7％	10％	-	0.3％		3	79.7％	-	-	0.3％	20％
4	89.7％	10％	-	0.3％		5	84.7％	15％	-	0.3％
6	79.7％	20％	-	0.3％		5	84.7％	15％	-	0.3％
6	79.7％	20％	-	0.3％		7	85.7％	10％	4％	0.3％
8	83.7％	10％	6％	0.3％		7	85.7％	10％	4％	0.3％
8	83.7％	10％	6％	0.3％		9	80.7％	15％	4％	0.3％
10	78.7％	15％	6％	0.3％		9	80.7％	15％	4％	0.3％
10	78.7％	15％	6％	0.3％		11	75.7％	20％	4％	0.3％
12	73.7％	20％	6％	0.3％		11	75.7％	20％	4％	0.3％
12	73.7％	20％	6％	0.3％		13	71.7％	20％	8％	0.3％

¹HIMONT CA53A

²EPOLENE E-43

³The polyether monoamine that contains 40 ethylene oxide units and 2.4 propylene oxide units generally has the structural formula shown in the JEFFAMINE  M-2070 in glossary, is called in Huntsman Corporation " XTJ-418 ".

⁴AMOCO 1016

Table 2B

	1	2	3	4	5	6	7
	1	2	3	4	5	6	7	Modulus in flexure, MPa	510	646	705	588	664	734	546
Yielding stress, MPa	15.8	19.8	21.4	18.7	20.6	22.7	17.2	Modulus in flexure, MPa	510	646	705	588	664	734	546
Yielding stress, MPa	15.8	19.8	21.4	18.7	20.6	22.7	17.2	Tensile elongation, %	666	666	666	666	666	484	531
Tensile strength, MPa	14.6	17.0	18.1	14.6	14.6	15.5	12.3	Tensile elongation, %	666	666	666	666	666	484	531
Tensile strength, MPa	14.6	17.0	18.1	14.6	14.6	15.5	12.3	Young's modulus, MPa	284	368	394	340	375	414	310
Hardness, Shore D	58	60	60	59	61	62	57	Young's modulus, MPa	284	368	394	340	375	414	310
Hardness, Shore D	58	60	60	59	61	62	57	Breach Izod shock strength, J/m	589	582	597	529	398	94	499
-30℃，J/m	65	47	38	38	37	37	40	Breach Izod shock strength, J/m	589	582	597	529	398	94	499
-30℃，J/m	65	47	38	38	37	37	40	Non-notch Izod shock strength, J/m	722	867	841	727	882	958	704
Dart impact performance								Non-notch Izod shock strength, J/m	722	867	841	727	882	958	704
Dart impact performance								Maximum load, J/m	1428	1589	1632	1486	1513	1529	1334
-30℃，J/m	3007	3335	3506	3290	3278	2610	889	Maximum load, J/m	1428	1589	1632	1486	1513	1529	1334
-30℃，J/m	3007	3335	3506	3290	3278	2610	889	Total energy, J	20.6	22.6	23.4	20.9	20.6	21.1	16.0
-30℃，J	39.4	39.3	44.6	43.0	38.5	18.0	3.7	Total energy, J	20.6	22.6	23.4	20.9	20.6	21.1	16.0
-30℃，J	39.4	39.3	44.6	43.0	38.5	18.0	3.7	Ductility/5	5	5	5	5	5	5	5
-30℃/5	5	4	5	5	4	0	0	Ductility/5	5	5	5	5	5	5	5

Table 2B (continuing)

	8	9	10	11	12	13
	8	9	10	11	12	13	Modulus in flexure, MPa	502	529	618	603	591	653
Yielding stress, MPa	16.4	16.9	18.6	18.8	18.5	19.6	Modulus in flexure, MPa	502	529	618	603	591	653
Yielding stress, MPa	16.4	16.9	18.6	18.8	18.5	19.6	Tensile elongation, %	208	245	170	138	37	43
Tensile strength, MPa	11.7	12.2	13.0	13.5	13.5	13.8	Tensile elongation, %	208	245	170	138	37	43
Tensile strength, MPa	11.7	12.2	13.0	13.5	13.5	13.8	Young's modulus, MPa	299	309	355	348	354	381
Hardness, Shore D	52	58	57	52	57	59	Young's modulus, MPa	299	309	355	348	354	381
Hardness, Shore D	52	58	57	52	57	59	Breach Izod shock strength, J/m	443	437	445	310	162	90
-30℃，J/m	46	35	36	28	25	22	Breach Izod shock strength, J/m	443	437	445	310	162	90
-30℃，J/m	46	35	36	28	25	22	Non-notch Izod shock strength, J/m	601	642	834	871	732	789
Dart impact performance							Non-notch Izod shock strength, J/m	601	642	834	871	732	789
Dart impact performance							Maximum load, J/m	1180	1255	1207	1263	1205	908
-30℃，J/m	760	2344	1505	1018	911	688	Maximum load, J/m	1180	1255	1207	1263	1205	908
-30℃，J/m	760	2344	1505	1018	911	688	Total energy, J	12.9	14.1	14.2	14.4	13.2	7.0
-30℃，J	3.2	12	6.3	3.3	3.1	3.1	Total energy, J	12.9	14.1	14.2	14.4	13.2	7.0
-30℃，J	3.2	12	6.3	3.3	3.1	3.1	Ductility/5	5	5	5	5	5	0
-30℃/5	0	0	0	0	0	0	Ductility/5	5	5	5	5	5	0

Table 2C

The bonding test of grid

Sample disc	S1	S2	S1	S2
Sample disc	S1	S2	S1	S2	Adhesive tape	3M ¹	3M	NICHIBAN	NICHIBAN
Sample	W/O IPA	W/O IPA	W/O IPA	W/O IPA	Adhesive tape	3M ¹	3M	NICHIBAN	NICHIBAN
Sample	W/O IPA	W/O IPA	W/O IPA	W/O IPA	PP ²	5％		2％
1	29％	67％	74％	92％	PP ²	5％		2％
1	29％	67％	74％	92％	2	66％	76％	81％	84％
3	61％	73％	78％	61％	2	66％	76％	81％	84％
3	61％	73％	78％	61％	4	100％	98％	100％	98％
5	96％	100％	100％	99％	4	100％	98％	100％	98％
5	96％	100％	100％	99％	6	85％	94％	91％	96％
7	100％	100％	100％	100％	6	85％	94％	91％	96％
7	100％	100％	100％	100％	8	100％	100％	100％	100％
9	100％	100％	100％	100％	8	100％	100％	100％	100％
9	100％	100％	100％	100％	10	100％	100％	100％	100％
11	100％	100％	100％	100％	10	100％	100％	100％	100％
11	100％	100％	100％	100％	12	100％	100％	100％	100％
13	100％	100％	100％	100％	12	100％	100％	100％	100％

¹Scotch Brand 2040

²Contrast

Embodiment 1-2 shows that the TPO with the reaction product modification of maleation polypropylene of the present invention and polyetheramine provides a kind of composition that can directly spray.But this sprayability is amazing and unanticipated, also is difficult for reaching commercial acceptable and directly sprays ability because be used for preparing the TPO of car body component such as bumper beam.So far for this reason, moulding car body component for the TPO basic mode that makes automobile can spray, and these parts will produce poisonous waste liquid stream like this with comprising attached dose of processing of increasing of lower molecular weight chlorinatedpolyethylene and solvent, must carry out suitable disposal, thereby increase the cost of parts.Perhaps, the method for available plasma irradiation or this parts surface of partial combustion is heat-treated these parts.This mode is also relatively more expensive, and because of mode batch between deviation and operator's error, the result is changeable.

According to the composition of enforcement of the present invention preparation with or without can directly spraying usually under the priming paint, the result is according to the described test procedure of the foregoing description 1-2, and lacquer bonding greater than about 75% is preferably greater than about 85%, more preferably greater than about 90%, most preferably greater than about 95%.

Composition prepared in accordance with the present invention available molding methods traditional, that the crowd knows under standard conditions is used to prepare moulded parts.For example can use the injection moulding process of standard.Some compositions of the present invention (blend) is surprisingly found out that in the injection moulding process of TPO based composition and use thereof in packaging its flowing property has had raising, like this when being expelled to melt composition in the mould, compare with the composition of polyetheramine useless, can use lower pressure.The desired shape of moulded parts becomes with the end-use of these goods.But the rubber injection moulding that for example contains the present composition prepares car body component such as bumper beam.

Embodiment 3

With methyl alcohol ethoxylation (mol ratio of ethylene oxide/methyl alcohol is about 43: 1); carry out propoxylation with about 3 mole propylene oxide subsequently; thereby how to make alcohol, analyze this how alcohol, but total acetylize equivalent (acetylatable) is 0.474meq/g (2110g/eq).The many alcohol of 1.0 Pounds Per Hours be somebody's turn to do, 1.25 Pounds Per Hours ammonia and the hydrogen of 42 Pounds Per Hours (STP) are joined in the tubular reactor that contains the 594g amination catalysis simultaneously.This reactor is remained under 208 ℃ and 2000 pounds/square inch (psig).Collect effluent, remove deammoniation, water and lightweight thing, analyze then, the result is as follows: but total acetylize equivalent is that 0.473meq/g, total amine are that 0.454meq/g and primary amine are 0.450meq/g.The polyether monoamine of gained contains 43 ethylene oxide units of having an appointment like this, and equivalent is about 2110.This polyether monoamine is referred to herein as " XTJ-418 ".

Embodiment 4

Preparation contains the blend of the polyether monoamine of embodiment 3, and its component and performance are shown in table 4A and 4B.In table 4A, use the composition that contains polypropylene, maleation polypropylene (HIMONT CA53A) and amine.In table 4B, use the TPO based composition and use thereof in packaging.In table 4A-4B, JEFFAMINE M-2070 refers to contain the polyether monoamine of 10 propylene oxide units and 32 ethylene oxide units.The data point of JEFFAMINE M-2070 is used for comparing with the data of XTJ-418.

Table 4A

The polypropylene-base composition

Maleation polypropylene (%)	20	20	20	20	20	20	30	30	30	30	30
Maleation polypropylene (%)	20	20	20	20	20	20	30	30	30	30	30	XTJ-418(％)	4		6		8		4		6		8
JEFFAMINE M-2070(％)		4		6		8		4		6		XTJ-418(％)	4		6		8		4		6		8
JEFFAMINE M-2070(％)		4		6		8		4		6		The binding property (%) of lacquer	14	42	56	53	80	40	65	50	52	43	92

Table 4B

The TPO based composition and use thereof in packaging

Maleation polypropylene (%)	10	10	15	15	15	20	20	20	20	20	20	20
Maleation polypropylene (%)	10	10	15	15	15	20	20	20	20	20	20	20	XTJ-418(％)	4	6	4		6		4		6		8
JEFFAMINE M-2070(％)				4		6		4		6		8	XTJ-418(％)	4	6	4		6		4		6		8
JEFFAMINE M-2070(％)				4		6		4		6		8	The binding property (%) of lacquer	100	100	100	90	100	89	100	70	100	90	100	96

Embodiment 4 shows, obtains the adhesion of coatings performance of excellence with the polyether monoamine of embodiment 3.The binding property that is to be understood that the XTJ-418 gained is at most 80% in table 4A, and the binding property of JEFFAMINE M-2070 is not higher than 53%.Will also be understood that in addition that in automobile industry from the angle of commerce, it is underproof being lower than 100% binding property.

Glossary

JEFFAMINE M-1000 JEFFAMINE M-2070 and JEFFAMINE M-2005Wherein R=H or CH ₃, m is about 3～32, n is about 10～32. JEFFAMINE D-2000, JEFFAMINE D-4000 With JEFFAMINE D-400

Wherein x is about 33 to D-2000, and x is about 68 to D-4000, and x is about 5.6 to D-400. JEFFAMINE ED-600, JEFFAMINE ED-900, JEFFAMINE ED -2001, JEFFAMINE ED-4000 and JEFFAMINE ED-6000Wherein for ED-600 b be about 8.5 and a+c be about 2.5, for ED-900 b be about 15.5 and a+c be about 2.5, for ED-20-1 b be about 40.5 and a+c be about 2.5, for ED-4000 b be about 86.0 and a+c be about 2.5, for ED-6000 b be about 132.0 and a+c be about 3.0. JEFFAMINE T-3000 With JEFFAMINE T-5000

Wherein for T-3000 x+y+z=50, for T-5000 x+y+z=83. JEFFAMINE ET-3000 X+y+z=57 wherein, a+b+c=4.

Claims

1. polyether monoamine, it contains 36～44 ethylene oxide units and 1～6 propylene oxide unit.

2. according to the polyether monoamine of claim 1, wherein the molecular weight of polyether monoamine is 2000～2200.

3. according to the polyether monoamine of claim 1, wherein polyether monoamine contains 40～43 ethylene oxide units and 2.4～3 propylene oxide units.

4. according to the polyether monoamine of claim 2, wherein polyether monoamine has following structural formula:

Wherein m is 36～44, and n is 1～6.

5. according to the polyether monoamine of claim 3, wherein m is 40～43, and n is 2.4～6.

6. according to the polyether monoamine of claim 3, its molecular weight is 2000～2200.

7. according to the polyether monoamine of claim 4, its molecular weight is 2000～2200.

8. composition, said composition comprises the reaction product of polypropylene and functionalization polypropylene and polyether monoamine, wherein polyether monoamine contains 36～44 ethylene oxide units and 1～6 propylene oxide unit.

9. composition according to Claim 8, wherein functionalization polypropylene is a maleation polypropylene.

10. composition according to Claim 8, wherein the molecular weight of polyether monoamine is 2000～2200.

11. composition according to Claim 8, wherein polyether monoamine contains 40～43 ethylene oxide units and 2.4～3 propylene oxide units.

12. composition according to Claim 8, wherein polyether monoamine has following structural formula:

Wherein m is 36～44, and n is 1～6.

13. composition according to Claim 8 comprises:

(a) polypropylene of 70wt%～80wt%;

(b) maleation polypropylene of 20wt%～30wt%; And

(c) polyether monoamine of 2wt%～10wt%,

Weight in composition is benchmark, and total amount is no more than 100%.

14. method for preparing the reaction product of maleation polypropylene and polyether monoamine, be included under the polyacrylic existence by in a mixing device, being 175～300 ℃ and the residence time to be in 25～300 seconds the process the each component fusion in temperature, thereby polyether monoamine is grafted on the maleation polypropylene, and wherein polyether monoamine contains 36～44 ethylene oxide units and 1～6 propylene oxide unit.

15. a composition that is used to prepare the molding automobile body components, said composition comprises:

Polypropylene;

Elastomerics;

And functionalization polypropylene and the reaction product that contains the polyether monoamine of 36～44 ethylene oxide units and 1～6 propylene oxide unit.

16. according to the composition of claim 15, wherein polyether monoamine contains 40 ethylene oxide units and 2.4～3 propylene oxide units.

17. according to the composition of claim 15, wherein polyether monoamine has following structural formula: M is 36 to 44, and n is 1 to 6.

18. according to the composition of claim 15, wherein functionalization polypropylene is a maleation polypropylene.

19. according to the composition of claim 15, wherein elastomerics is an ethylene propylene rubber.

20. according to the composition of claim 15, wherein functionalization polypropylene is a maleation polypropylene, its amount is 5wt%～40wt%, and the amount of polyether monoamine is 2wt%～10wt%, is benchmark with the composition weight.

21., wherein do not have the amine beyond the polyether monoamine and do not have alkene and the multipolymer of maleic anhydride according to the composition of claim 15.

22. according to the composition of claim 15, wherein the binding property of the lacquer of said composition is greater than 95%.

23., also comprise the glass filler of 40wt% at the most according to the composition of claim 15.

24. a manufacture is the automobile body components form, it makes by the composition injection moulding that will comprise following component:

Polypropylene;

Ethylene/propylene rubber; And

Maleation polypropylene and the reaction product that contains the polyether monoamine of 36～44 ethylene oxide units and 1～6 propylene oxide unit.

25. a method for preparing the automobile body components of spraying comprises:

The blend injection moulding that will comprise the reaction product of polypropylene, ethylene/propylene rubber and maleation polypropylene and polyether monoamine prepares the molding automobile body components, and wherein polyether monoamine contains 36～44 ethylene oxide units and 1～6 propylene oxide unit; With

The automobile body components of spraying molding.

26. parts according to claim 25 preparation.

27. a production is used to prepare the method for compositions of automobile body components, comprise polypropylene, maleation polypropylene and the polyether monoamine that contains 36～44 ethylene oxide units and 1～6 propylene oxide unit are 175～300 ℃ and make maleation polypropylene and polyether monoamine forms compounding under the condition of reaction product in temperature in forcing machine, thereby obtain the composition of compounding.

28. according to the method for claim 27, wherein in the compounding process and in the composition of compounding, have rubber.

29. a blended composition that can be used for preparing moulded parts, it comprises:

Polypropylene;

Filler;

30., also comprise ethylene/propylene rubber according to the composition of claim 29.

31. according to the composition of claim 29, wherein filler is a glass filler, and its amount is at most the 40wt% of said composition.