CN1189846A - Propylene polymer compsns. having improved impact strength - Google Patents
Propylene polymer compsns. having improved impact strength Download PDFInfo
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- CN1189846A CN1189846A CN96195194A CN96195194A CN1189846A CN 1189846 A CN1189846 A CN 1189846A CN 96195194 A CN96195194 A CN 96195194A CN 96195194 A CN96195194 A CN 96195194A CN 1189846 A CN1189846 A CN 1189846A
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Abstract
Crystalline propylene polymer compositions having improved impact strength and improved clarity are disclosed. The composition is prepared by melt blending a propylene polymer, e.g., polypropylene, and from about 1 to 35 wt.% of an elastomeric interpolymer of a C4 to C8 isomonoolefin, e.g., isobutylene, and a para-alkystyrene comonomer, e.g., para-methylstyrene. The interpolymer preferably contains a benzylic functional group such as halogen (bromine). The composition may also contain from about 0.5 to 15 wt.% of the amide reaction product of an organic acid-grafted propylene polymer, e.g., maleic anhydride grafted polypropylene, and a polyfunctional primary amine.
Description
Technical field
The present invention relates to have the polypropene composition of improved shock strength and improved optical transparence.
Background technology
Propene polymer, for example crystalline polypropylene or have about at the most 20%wt (weight) C
2Or C
4-C
8The crystalline propylene copolymer of α-monoolefine (as ethene) becomes fragile when low temperature (brittle point is at 0 ℃-20 ℃), and shock strength is poor.Generally speaking, polypropylene is lower than about 1ft.-lb/in. in the breach Izod shock strength that room temperature shows.
Known in the prior art, polypropylene and a small amount of elastomer polymer such as natural rubber or GRS blend rubber can be reduced polyacrylic brittle point, described in English Patent UK No.856793.
English Patent UK No.950551 is open, by forming isotactic polypropylene and about 28.5%wt polyisobutene and the poly blend of about at the most 5%wt at the most, can improve the impact property of isotactic polyprophlene.U.S. Pat No.3562790 discloses the blend based on polypropylene, about 2%-15%wt polyethylene (or multipolymer of ethene and different alpha-olefins) and the elastomeric tertiary mixture of about 2%-20%wt ethylene/propene/non-conjugated diene, and it has the improved shock strength and the transparency.U.S. Pat No.4500681 discloses the ternary blends of the multipolymer that contains 20%-65%wt isotactic polyprophlene, 20%-60%wt isobutene polymer (as polyisobutene, isoprene-isobutylene rubber or halogenated isoprene-isobutylene rubber) and about 7%-40%wt ethene and esters of unsaturated carboxylic acids (as vinyl-acetic ester).
Similarly, EP-A 214945 discloses the polypropylene film material with improved shock strength, and it is based on the blend of polypropylene with a small amount of one or more new LDPE (film grade)s, polybutene, polyisobutene and/or ethene and methyl acrylate copolymer.
Though many such compositions have improved the impact property of propene polymer to a certain extent, therefore and reduced temperature limit of brittleness, but also damaged other performance simultaneously, for example, contain polyisobutene or polyolefine such as poly blend has reduced optical transparence, the physicals of other blend such as stiffness and workability reduce.In addition, can infringement virgin pp inherent good tensile strength and modulus properties in blend with relatively large polymer-modified of polypropylene blending.
U.S. Pat No.5013793,5051477 and 5051487 discloses the polymer composition of dynamically vulcanizable, and it is based on the blend of elastomerics iso-butylene/p-methylstyrene multipolymer (preferred halogenated copolymers), one or more olefin polymers and iso-butylene/p-methylstyrene multipolymer vulcanization system.Said composition is solidified under the high shear mixing condition, and formation solidified elastomerics fine particle is scattered in the dispersion in the olefin polymer matrix.
The present invention's general introduction
The invention provides have high impact, thermoplastic propene's polymer composition of good transparency and good workability, it comprises the blend of following component:
A) crystalline propene polymer; With
B) contain the C to ring-alkylated styrenes of the 0.5%-20%mol that has an appointment (mole) copolymerization
4-C
7The multipolymer of isomonoolefin,
The amount of described multipolymer in described composition is the about 35%wt of about 1%-.
The present invention also provides the method for the physicals of the composition that a kind of improvement contains crystalline propene polymer, it comprises, under the temperature in about 150 ℃ of-250 ℃ of scopes, with propene polymer with in the C that contains the 0.5%-20%mol copolymerization of having an appointment of the about 35%wt of the about 1%-of polymer content to ring-alkylated styrenes
4-C
7The isomonoolefin copolymers melting mixing is until forming even blend.
Isomonoolefin copolymers also can comprise functionalized multipolymer, and it is to replace the hydrogen atom on a part of benzyl to prepare by functional group such as methacrylic ester, halogen atom or other functional group.
The present composition also can contain the other modifier polymer of the about 15%wt of the 0.5%-that has an appointment, and it is the amidate action product of following material:
(i) contain the modification crystalline propene polymer of grafted unsaturated organic compound, this unsaturated compound is selected from unsaturated carboxylic acid, unsaturated carboxylic acid anhydrides and composition thereof; And
The multiple functional radical primary amine that (ii) contains a primary amino and at least one hydroxyl, secondary amino group or uncle's amino.
The invention provides the composition of crystalline propene polymer, it has improved impact property, the good workability and the good optical transparency, has kept propene polymer inherent good tensile strength and modulus properties simultaneously again.
Detailed description of the present invention
In the present composition, comprise polypropylene and propylene and the copolymerizable C of 20%wt at the most as the crystalline propene polymer of main ingredient
2Or C
4-C
8Monoolefine, the crystalline copolymer of ethene most preferably.These polymkeric substance are known, and can be by method preparation as known in the art, for example, in the presence of so-called " ziegler-natta " transition-metal catalyst (as the combination of transition metal halide and trialkyl aluminium compound), make propylene or propylene/monoolefine polymerization of mixtures.Also can in the presence of the luxuriant catalyst system of containing metal, polymerization prepare propene polymer.The preferred propylene polymers that is used for the present invention is about 0.1-1000, more preferably from about 0.5-100g/10 minute at 230 ℃, melt flow rate during 2.16kg load.
The C that is used for the present invention
4-C
7Isoolefine/to alkylstyrene copolymers is C
4-C
7Isomonoolefin such as iso-butylene and contain at least about 80%wt, more preferably at least about the elastomerics random copolymers to ring-alkylated styrenes comonomer such as p-methylstyrene of 90%wt para-isomeride comprise also that wherein the alkyl substituent that exists to the small part styrene monomer unit contains halogen atom or other functional group's functionalized multipolymer.Preferable material can be characterized by the isobutylene copolymers that contains random following monomer units of arranging in main polymer chain:
In the formula, R and R ' are hydrogen independently of each other, low alkyl group, preferred C
1-C
7Alkyl, X are functional group such as halogen atom.Preferred R and R ' are hydrogen.About at the most 60%mol can be the functionalized structure shown in the formula (2) to ring-alkylated styrenes in copolymer structure.
When not having monomeric unit shown in the formula 2, then the isomonoolefin copolymers right and wrong are functionalized, and promptly it is an isomonoolefin and random copolymers to ring-alkylated styrenes.Most preferred this multipolymer is the have an appointment iso-butylene of the about 20%mol p-methylstyrene of 0.5%-and the multipolymer of p-methylstyrene of random copolymerization in main polymer chain.
When having monomeric unit shown in the formula 2, then isomonoolefin copolymers is the terpolymer that contains 0.5%-60%mol functionalized monomer unit 2 (based on the content of fragrant monomer unit 1 and 2) of having an appointment at least.Functional group X can be a halogen atom, perhaps other functional group who introduces with the halogen atom on other group nucleophilic substitution benzyl is as alkoxyl group, phenoxy group, carboxylic acid ester groups, thiol group, thioether group, thiocarbamate base, dithiocarbamate groups, thioureido, xanthogenic acid ester group, cyano group, propanedioic acid ester group, amido, amide group, carbazyl, adjacent benzoylimino base, dimaleoyl imino, cyanate ester based and their mixture.Isomonoolefin copolymers that these are functionalized and preparation method thereof is described in greater detail in the U.S. Patent No. 5162445, incorporates whole disclosures of the document into this paper by reference here.
The functionalized material of the most useful this type of is to contain the iso-butylene of the about 20%mol p-methylstyrene of the 0.5%-that has an appointment and the elastomerics random copolymers of p-methylstyrene, wherein the methyl substituents on the benzyl rings of about 60%mol contains acrylate or methacrylate based at the most, perhaps bromine or chlorine atom, preferred bromine atoms.These polymkeric substance have and distribute basic the composition uniformly, make 95%wt at least polymkeric substance to ring-alkylated styrenes content this polymkeric substance on average to ring-alkylated styrenes content up and down in 10% scope.Preferred polymkeric substance also has narrow molecular weight distribution, Mw/Mn less than about 5, be more preferably less than about 2.5, preferred viscosity-average molecular weight is in about 2000000 scopes of about 200000-, and preferred number-average molecular weight is in about 750000 scopes of about 25000-(by gel permeation chromatography).
These multipolymers can be prepared as follows: use lewis acid catalyst to make monomer mixture carry out slurry polymerization, subsequently halogen and radical initiator for example heating and/or illumination and/or chemical initiator in the presence of, halogenation in solution, preferred bromination.
Preferred multipolymer is the multipolymer of bromination, and it generally contains the about 5%nol brooethyl of the 0.1%-that has an appointment, and the overwhelming majority wherein is single brooethyl, and the amount of dibromo methyl substituents is less than 0.05%mol in the multipolymer.Preferred multipolymer contains in the about 2.5%wt of the about 0.05%-of multipolymer weight, 0.05%-0.75%wt bromine most preferably from about, and it does not have ring to go up halogen atom on halogen atom or the main polymer chain basically.
These multipolymers, they the preparation method, they curing and be described in greater detail among the above-mentioned document US No.5162445 by their deutero-grafting or functionalized polymkeric substance.
In prolylene polymer composition, based on the polymer content meter of composition, the preferred add-on of multipolymer is about 5%-35%wt, more preferably from about 10%-25%wt.Another preferred range is 1%-20%wt, more preferably 10%-20%wt.
In another embodiment of the present invention, by adding the additive polymer of the amidate action product that comprises following material on a small quantity, can further improve the consistency and the physicals of the blend composition of propene polymer and multipolymer: (i) crystalline propene polymer of modification, with respect to every gram polymkeric substance, it contains along the about 0.5-0.001mmol of main polymer chain grafted (mmole) unsaturated organic acid or acid anhydrides; The multiple functional radical primary amine that (ii) has a primary amino and at least one hydroxyl, secondary amino group or uncle's amino.
Preferred modified propylene polymer is by making polypropylene and unsaturated organic acid or acid anhydrides at the crystalline polypropylene that is modified in the conversion zone reaction in the presence of the radical initiator, under the graft reaction condition.
Described carboxylic acid can be monobasic or polycarboxylic acid, preferably has 3-12 carbon atom.For example, unsaturated carboxylic acid can be toxilic acid, fumaric acid, citraconic acid, methylfumaric acid, methylene-succinic acid, himic acid, acetylenedicarboxylic acid and composition thereof.Preferred carboxylic acid is a toxilic acid.Suitable acid anhydrides comprises maleic anhydride, citraconic anhydride, itaconic anhydride and himic acid acid anhydride.Preferred acid anhydrides is a maleic anhydride.
In polymers grafted of the present invention, the amount of acid or anhydride component can be about 0.5-0.001, preferably about 0.2-0.002,0.1-0.005mmol/g polymers grafted product more preferably from about.
Polymers grafted is prepared as follows: propene polymer is contacted with grafting agent, and initiator can be compound or radiation.Suitable radical initiator comprises: (1) but thermolysis forms the compound of free radical, as azo-compound or organo-peroxide; (2) produce the compound of free radical by non-by the use of thermal means such as photochemistry or oxide-reduction method; (3) itself has the compound of free radical feature, as oxygen molecule; Or (4) electromagnetic radiation, as X-ray, electron beam, visible light, ultraviolet ray.
Suitable organo-peroxide comprises hydroperoxide, dialkyl, peroxidation diacyl, peresters, crosses two carbonic ethers, ketal peroxide, ketone peroxide and organic sulfonyl-peroxide.
Preferred radical initiator is that transformation period under temperature of reaction is less than 1/10 the organo-peroxide of employed reaction/residence time.
When radical initiator was compound, the suitable mol ratio of radical initiator compound and grafted monomer can be 0.001: 1 to 1: 1, preferred 0.01: 1 to 0.1: 1.
Graft reaction can not have thinner or carry out in the presence of thinner.
When there was thinner in conversion zone, suitable diluents comprised aliphatic saturated hydrocarbon, aromatic hydrocarbon and full halogenated hydrocarbon.
Preferably, the graft reaction of preparation graftomer carries out in the presence of the thinner and in fusion mutually not having, and propene polymer wherein is molten state.The selective reaction temperature is to be adapted to used initiator.
In an embodiment preferred; graft reaction carries out in twin screw extruder; it has the screw unit that has following function successively: (i) by shearing and extruding is heated to polymkeric substance or near desired reaction temperature; (ii) in temperature of reaction or near under the temperature of reaction polymkeric substance being mixed with grafting agent; the polymkeric substance that (iii) will contain grafting agent mixes with initiator; (iv) provide the suitable residence time to carry out graft reaction; (v) unreacted grafting agent and the sharp by product of initiation are discharged; (vi) with required stablizer or additive mixes and (vii) will react; getting rid of by product and stabilized polymkeric substance sends in suitable processing unit (plant) such as the tablets press.
The proper method for preparing these modified polypropene graftomer is disclosed among the U.S. Pat No.3862265, incorporates its whole disclosures into this paper by reference here.
Then, under certain reaction conditions, the propene polymer of graft modification is contacted with stoichiometric at least above-mentioned multiple functional radical primary amine, make the carboxylic-acid functional radical reaction to small part amine and the propene polymer skeleton form acid amides, can make the amide derivatives of the propene polymer of graft modification.Reaction is not preferably having in the presence of the thinner, is carrying out in 150 ℃-250 ℃ melt.
In composition, add to promote the catalyzer of electrophilic substitution reaction, can further improve the consistency of three blend of components of the propene polymer of the isomonoolefin copolymers that comprises propene polymer, functionalized (for example halogenation) and amidation modification.The example of this class catalyzer has zinc oxide, magnesium oxide, zinc bromide, iron(ic) chloride etc.Based on the content of the isomonoolefin copolymers of functionalized in the composition, for example bromination, the add-on of these catalyzer is the about 1.5%wt of about 0.01%-, more preferably from about 0.05%-0.5%wt.
Based on the polymer content in the composition, the present composition contains the 1%-35%wt that has an appointment, the about 30%wt isomonoolefin copolymers of 5%-more preferably from about usually, and the consumption of the propene polymer of graft modification (if using in composition) in composition is the about 15%wt of about 0.5%-, the about 10%wt of 1%-more preferably from about.
For further improving the performance of composition, can also other thermoplastic polymer and propene polymer and the isomonoolefin copolymers blend of the 20%wt of composition will be at most.These polymkeric substance comprise polyethylene, ethylene/propene copolymer, ethylene/propene and non-conjugated diene such as Dicyclopentadiene (DCPD), 1, the terpolymer of 4-hexadiene or ethylidene norbornene, the multipolymer of ethene and vinyl-acetic ester or (methyl) lower alkyl acrylate, divinyl and cinnamic multipolymer and segmented copolymer, or the like.
The present composition also can comprise significant quantity other be usually used in component in the polypropene composition, comprise oxidation inhibitor, pigment, tinting material, filler, plasticity etc.
But the polymeric constituent in the present composition and the composition can not cure or be crosslinked, therefore, does not contain in the composition and can make composition and component thereof such as isomonoolefin/to alkylstyrene copolymers solidified reagent.
Use any suitable molten load in mixture to put as Banbury mixer, Bradley originally step on (Braben-der) mixing machine or mixing machine/forcing machine mixes all polymeric constituents under the shear-mixed condition, can make blend.Preferred molten mixed temperature is about 150 ℃-Yue 250 ℃, and more preferably from about 170 ℃-Yue 230 ℃, mixing time should be enough to obtain the homogeneous dispersion of polymeric constituent in propylene polymer matrix, is generally about 0.5-4 minute.
The following example is used to illustrate the present invention.Used following component in an embodiment:
PP-5052: the alfon that exxon chemical company (Exxon Chemical Company) is made is that the melt flow rate of measuring under the 2.16kg is 1.3g/10 minute (ESCORENE at 230 ℃, load
TM).
PP-1042: the alfon that exxon chemical company is made is that the melt flow rate of measuring under the 2.16kg is 1.9g/10 minute (ESCORENE at 230 ℃, load
TM).
I-PMS-1: the multipolymer of iso-butylene and p-methylstyrene (PMS), the content of PMS is about 2.2%mol, mooney viscosity is 50 (ML, 1+8,125 ℃).
I-PMS-2: the multipolymer of iso-butylene and p-methylstyrene (PMS), the content of PMS is about 5%wt, mooney viscosity is 35 (ML, 1+8,125 ℃).
Br-IPMS-1: the iso-butylene of bromination/PMS multipolymer, PMS content is about 1.5%mol, is about 0.7%mol to the brooethyl styrene content, mooney viscosity is 46 (ML, 1+8,125 ℃).
Br-IPMS-2: the iso-butylene of bromination/PMS multipolymer, PMS content is about 5%wt, and the content of bromine is about 0.5%mol, and mooney viscosity is 35 (ML, 1+8,125 ℃).
BrIPMS (ZnO): with the Br-IPMS-2 of about 1%wt ZnO powder dilution.
MAE-XP-3: the iso-butylene of methacrylated/PMS multipolymer, PMS content are 5%wt, and methacrylate content is 0.3%mol, and mooney viscosity is 35 (ML, 1+8,125 ℃).
MAE-XP-7: the iso-butylene of methacrylated/PMS multipolymer, PMS content are 5%wt, and methacrylate content is 0.7%mol, and mooney viscosity is 35 (ML, 1+8,125 ℃).
PIB-L-120: isobutylene homo, viscosity-average molecular weight Wt are 166000, exxon chemical company manufacturing (VISTANEX
TM).
Additive B: the product that melt flow rate (2.16kg load, 190 ℃) makes for the polypropylene (maleic anhydride content is 1.0%wt) of 184g/10 minute maleic anhydride graft and 1.5mol (with respect to the maleic anhydride of every mole of existence) multiple functional radical primary amine reaction.Be reflected at Bradley and originally step in the mixing machine and carry out at 210 ℃, the reaction times is 3 minutes.With the granulation of refrigerative product, and with pellet backflow dichloromethane extraction, to remove unreacted multiple functional radical primary amine.
Additive B-1: multiple functional radical primary amine wherein is 2-(the amino ethylamino of a 2-) alcoholic acid additive B.
Additive B-2: multiple functional radical primary amine wherein is the additive B of 1-(2-amino-ethyl) piperazine.
Use 15 short tons of Boy
RInjection moulding machine is shaped to test rod with the pellet of extruding of subject composition, carries out Mechanics Performance Testing.Carry out performance test according to following ASTM method:
Testing method
IZOD shock strength ASTM D-256
Modulus in flexure ASTM D-790
Yield strength ASTM D-638
Elongation at yield ASTM D-638
Comparative Examples 1
At Boy
TMOn the injection moulding machine with Escorene
RPP 5052 makes 5 " * 0.5 " * 0.125 " test rod.After 24 hours, measure the breach Izod shock strength (ASTM D-256) and the modulus in flexure (ASTM D-790) of these samples, the results are shown in Table 1, is used for contrasting with the embodiment of the invention.
Embodiment 2 and 3
With Escorene
RPP 5052 (200g) adds the 300ml Bradley of preheating and originally steps in the mixing machine, and is that the stirring of 60rpm rises to 170 ℃ with temperature with rotating speed.Add I-PMS-1 or Br-IPMS-1 multipolymer (50g), continue to mix 3 minutes.Blend is discharged, make it be cooled to room temperature and granulation.Described in Comparative Examples 1, make sample and measure their physicals.Test result is listed in the table 1.The result shows, compares with the polypropylene of not blend, and the room temperature Izod shock strength that contains the blend of iso-butylene/PMS multipolymer has moderate raising, contains the increasing significantly of blend of iso-butylene/BrPMS multipolymer.
Embodiment 4 and 5
With Escorene
RPP 5052 (180g) adds the 300ml Bradley of preheating and originally steps in the mixing machine, and is that the stirring of 60rupm rises to 170 ℃ with temperature with rotating speed.Add iso-butylene/BrPMS multipolymer (50g), add additive B-1 or B-2 (20g) subsequently.Continue to mix 3 minutes.Discharge blend, it is cooled to room temperature and granulation.The physicals of described in comparative example 1, making sample and testing them.The results are shown in Table 1.
Compare with the blend that does not have additive (embodiment 3), add additive B 1 and B2 (embodiment 4 and 5) and make the room temperature Izod shock strength of blend higher.Table 1
| Embodiment forms (wt%) | ????1 | ????2 | ????3 | ????4 | ????5 |
| ????PP?5052 | ????100 | ????80 | ????80 | ????72 | ????72 |
| ????I-PMS-1 | ????- | ????20 | ????- | ????- | ????- |
| ????Br-IPMS-1 | ????- | ????- | ????20 | ????20 | ????20 |
| Additive B-1 | ????- | ????- | ????- | ????8 | ????- |
| Additive B-2 | ????- | ????- | ????- | ????- | ????8 |
| Breach IZOD (Ft/LB/in)+23 ℃-20 ℃ | ????0.5 ????- | ????3.2 ????- | ????11.9 ????0.4 | ????14.2 ????1.0 | ????15.2 ????0.6 |
| Modulus in flexure (kpsi) | ????153 | ????105 | ????105 | ????112 | ????114 |
Embodiment 6-33
As mentioned above, other composition of prescription shown in the preparation table 2, difference is to be blended in about 200 ℃, to carry out in mixing forcing machine.The test result of the physicals of these compositions is also listed in the table 2.
Data in the table 2 show, compare with isobutylene homo, and the multipolymer of iso-butylene and p-methylstyrene and derivative thereof are more effective polypropylene impact strength modifiers.
In table 2, embodiment 6 is results of unmodified polypropylene (PP1042 of exxon chemical company).Embodiment 7-11 is the result with the blend of polyisobutene.Though the breach Izod shock strength under the room temperature increases, the degree that increases will be lower than with the similar blend (embodiment 12-16) of iso-butylene/p-methylstyrene multipolymer.The effect that iso-butylene/p-methylstyrene is copolymer-modified dose is 20% and especially obviously (embodiment 15 and 16 was contrasted as can be seen with embodiment 10 and 11) in 25% o'clock in blend concentration.The multipolymer of the effect that the iso-butylene of bromination/p-methylstyrene multipolymer (embodiment 30-33) reaches and bromination not quite.
Show certain toughening effect with the blend (embodiment 17-20 and 21-24) of the ester modified iso-butylene/p-methylstyrene multipolymer of two kinds of methacrylic acids, between isobutylene homo and unmodified iso-butylene/p-methylstyrene multipolymer.
The breach Izod shock strength that contains the composition of Zinc oxide doped bromination iso-butylene/p-methylstyrene multipolymer compares the not properties-correcting agent poor (comparing embodiment 28 and 32 is as can be seen) of blending when 20% blend concentration, but 25% o'clock both suitable (comparing embodiment 29 and 33 as can be seen).This shows, uses crosslinked Br-IPMS elastomerics can damage the shock strength of polypropylene/Br-IPMS multipolymer.
Except the quantitative data in the table 2, also find, compare to have excellent optical transparence with the blend that iso-butylene/the p-methylstyrene multipolymer makes with the blend that makes by isobutylene homo.This better is consistent (though this is beat all) with this blend and polyacrylic consistency.Table 2
Table 2 (continuing)
| Embodiment | ???6 | ??7 | ???8 | ???9 | ??10 | ??11 | ??12 | ??13 | ??14 | ??15 | ??16 | ??17 | ??18 | ??19 | |
| Form | |||||||||||||||
| PP-1042 | ??100 | ??95 | ??90 | ??85 | ??20 | ??25 | ??95 | ??90 | ??85 | ??80 | ??75 | ??95 | ??90 | ??85 | |
| PIB-L?120 | ??5 | ??10 | ??15 | ??20 | ??25 | ||||||||||
| I-PMS-2 | ???5 | ??10 | ??15 | ??20 | ??25 | ||||||||||
| MAE-XP3 | ???5 | ??10 | ??15 | ||||||||||||
| MAE-XP7 | |||||||||||||||
| Br-IPMS-ZnO | |||||||||||||||
| Br-IPMS-2 | |||||||||||||||
| NI-RT | ft-lb/in | ??0.8 | ??1.0 | ??1.2 | ??1.7 | ??2.1 | ??3.4 | ??0.8 | ??1.5 | ??3.4 | ??10.7 | ??11.8 | ??1.0 | ??1.3 | ??1.9 |
| NI-0℃ | ft-lb/in | ??0.36 | ??0.50 | ??0.56 | ??0.65 | ??0.86 | ??0.34 | ??0.34 | ??0.47 | ??0.63 | ??0.77 | ??0.33 | ??0.37 | ??0.51 | |
| NI-10℃ | ft-lb/in | ??0.33 | ??0.37 | ??0.55 | ??0.59 | ??0.70 | ??0.33 | ??0.31 | ??0.36 | ??0.55 | ??0.53 | ??0.32 | ??0.37 | ??0.36 | |
| Embodiment | ????20 | ????21 | ????22 | ????23 | ????24 | ????25 | ????26 | ????27 | ????28 | ????29 | ????30 | ????31 | ????32 | ????33 | |
| Form | |||||||||||||||
| ?PP-1042 | ????80 | ????95 | ????90 | ????85 | ????80 | ????95 | ????90 | ????85 | ????80 | ????75 | ????90 | ????85 | ????80 | ????75 | |
| ?PIB-L?120 | |||||||||||||||
| ?I-PMS-2 | |||||||||||||||
| ?MAE-XP3 | ????20 | ||||||||||||||
| ?MAE-XP7 | ????5 | ????10 | ????15 | ????20 | |||||||||||
| ?Br-IPMS-ZnO | ????5 | ????10 | ????15 | ????20 | ????25 | ||||||||||
| ?Br-IPMS-2 | ????10 | ????15 | ????20 | ????25 | |||||||||||
| ?NI-RT | ?ft-lb/in | ????5.2 | ????1.1 | ????1.5 | ????2.4 | ????3.5 | ????1.0 | ????1.2 | ????1.5 | ????2.4 | ????11.3 | ????1.7 | ????2.1 | ????9.6 | ????12.2 |
| ?NI-0℃ | ?ft-lb/in | ????0.60 | ????0.33 | ????0.5 | ????0.75 | ????0.95 | |||||||||
| ?NI-10℃ | ?ft-lb/in | ????0.56 | ????0.34 | ????0.36 | ????0.56 | ????0.76 | |||||||||
Claims (20)
1. thermoplastic polymer composition, it comprises the blend of following component:
A) crystalline propene polymer; With
B) contain the C to ring-alkylated styrenes of the about 20%mol copolymerization of the 0.5%-that has an appointment
4-C
7The multipolymer of isomonoolefin,
Based on the polymer content meter in the composition, the amount of this multipolymer is the about 35%wt of about 1%-in the described composition.
2. according to the composition of claim 1, wherein, described propene polymer is selected from polypropylene and propylene and about at the most 20%wt C
2Or C
4-C
8The multipolymer of α-monoolefine.
3. according to the composition of claim 1, wherein, described isomonoolefin is an iso-butylene, and described be p-methylstyrene to ring-alkylated styrenes.
4. according to the composition of claim 1, wherein, the amount of described multipolymer in composition is the about 30%wt of about 5%-.
5. according to the composition of claim 1, wherein, described multipolymer comprises the polymkeric substance that contains along the unitary iso-butylene of following fragrant monomer of polymer chain random arrangement:
In the formula, R and R ' are hydrogen atom or C independently of each other
1-C
4Alkyl, X are the functional groups.
6. according to the composition of claim 5, wherein, account for about 0.5%-60%mol in the unitary total amount of described fragrant monomer that the monomeric unit of the described X of containing exists in described multipolymer.
7. according to the composition of claim 5, wherein, X is a halogen atom.
8. according to the composition of claim 7, wherein, R and R ' all are hydrogen atoms, and X is a bromine, and the amount of bromine in described multipolymer is less than about 2.5%wt.
9. composition according to Claim 8, wherein, the amount of bromine in described multipolymer is the about 0.75%wt of about 0.05%-.
10. according to the composition of claim 7, it also contains the additive polymer of the about 15%wt of 0.5%-that has an appointment, and it comprises the amidate action product of following material:
(i) contain the modification crystalline propene polymer of grafted unsaturated organic compound, described unsaturated organic compound is selected from unsaturated carboxylic acid, unsaturated carboxylic acid anhydrides and composition thereof; With
The multiple functional radical primary amine that (ii) has a primary amino and at least one hydroxyl, secondary amino group or uncle's amino.
11. according to the composition of claim 10, wherein, described propene polymer is a polypropylene.
12. according to the composition of claim 10, wherein, described unsaturated organic compound is a maleic anhydride.
13. according to the composition of claim 10, wherein, described primary amine is selected from 2-(the amino ethylamino of 2-) ethanol and 1-(2-amino-ethyl) piperazine.
14. according to the composition of claim 1, wherein, the amount of described multipolymer in composition is about 10%-25%wt.
15. according to the composition of claim 1, wherein, the amount of described multipolymer in composition is about 1%-20%wt.
16. according to the composition of claim 1, wherein, the amount of described multipolymer in composition is about 10%-20%wt.
17. a method for preparing thermoplastic polymer blend, it comprises:
(a) make the C that contains the 0.5%-20%mol copolymerization of having an appointment that comprises crystalline propene polymer and about 1%-35%wt to ring-alkylated styrenes
4-C
7The mixture of isomonoolefin copolymers; And
(b) temperature in about 150 ℃ of-250 ℃ of scopes is molten mixed with described mixture, until obtaining uniform blend.
18. according to the method for claim 17, wherein, described multipolymer comprises the iso-butylene/p-methylstyrene multipolymer of bromination, the content of bromine is the about 0.75%wt of 0.05%-.
19. according to the method for claim 18, wherein, described mixture also contains the about 15%wt additive polymer of the 0.5%-that has an appointment, it comprises the amidate action product of following component:
(i) contain along the crystalline propene polymer of the modification of polymer chain grafted unsaturated organic compound, described unsaturated compound is selected from unsaturated carboxylic acid, unsaturated carboxylic acid anhydrides and composition thereof; And
The multiple functional radical primary amine that (ii) has a primary amino and at least one hydroxyl, secondary amino group or uncle's amino.
20. a moulded products, it is made by the thermoforming of the composition of claim 1.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN96195194A CN1189846A (en) | 1995-06-30 | 1996-06-28 | Propylene polymer compsns. having improved impact strength |
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US08/497,486 | 1995-06-30 | ||
| CN96195194A CN1189846A (en) | 1995-06-30 | 1996-06-28 | Propylene polymer compsns. having improved impact strength |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN1189846A true CN1189846A (en) | 1998-08-05 |
Family
ID=5129044
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN96195194A Pending CN1189846A (en) | 1995-06-30 | 1996-06-28 | Propylene polymer compsns. having improved impact strength |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN1189846A (en) |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1304457C (en) * | 2002-09-24 | 2007-03-14 | 重庆大学 | Diamine modified poly-latic acid, method for preparing same and use thereof |
| CN1329416C (en) * | 2002-09-09 | 2007-08-01 | 普瑞曼聚合物有限公司 | Modified propylene polymer and polyolefin resin composition |
| CN100377901C (en) * | 2004-05-10 | 2008-04-02 | 丰田自动车株式会社 | Control device for vehicular transmission mechanism |
| CN112724610A (en) * | 2019-10-28 | 2021-04-30 | 中国石油化工股份有限公司 | Reinforced modified PET polyester blend and polyethylene terephthalate blended plastic |
-
1996
- 1996-06-28 CN CN96195194A patent/CN1189846A/en active Pending
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1329416C (en) * | 2002-09-09 | 2007-08-01 | 普瑞曼聚合物有限公司 | Modified propylene polymer and polyolefin resin composition |
| CN1304457C (en) * | 2002-09-24 | 2007-03-14 | 重庆大学 | Diamine modified poly-latic acid, method for preparing same and use thereof |
| CN100377901C (en) * | 2004-05-10 | 2008-04-02 | 丰田自动车株式会社 | Control device for vehicular transmission mechanism |
| CN112724610A (en) * | 2019-10-28 | 2021-04-30 | 中国石油化工股份有限公司 | Reinforced modified PET polyester blend and polyethylene terephthalate blended plastic |
| CN112724610B (en) * | 2019-10-28 | 2022-07-12 | 中国石油化工股份有限公司 | Reinforced modified PET polyester blend and polyethylene terephthalate blended plastic |
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