CN1420903A

CN1420903A - Resin pellet with excellent nontackiness and process for producing same

Info

Publication number: CN1420903A
Application number: CN01807376A
Authority: CN
Inventors: 守屋悟; 木村友彦
Original assignee: Mitsui Chemical Industry Co Ltd
Current assignee: Mitsui Chemicals Inc; Mitsui Chemical Industry Co Ltd
Priority date: 2000-03-27
Filing date: 2001-03-26
Publication date: 2003-05-28
Also published as: JP2001342259A; KR20020086702A; WO2001072876A1

Abstract

A process for producing resin pellets having excellent nontackiness, characterized by coating the surface of pellets of at least one resin selected from the following group of copolymers having a modulus in tension (23 DEG C) of 1,600 MPa or lower with both at least one liquid having a specific dynamic viscosity and a specific surface tension (e.g., dimethylpolysiloxane) and a fine powder of at least one organic substance (e.g., calcium stearate) or of silica having an average particle diameter of 50 mum or smaller. Examples of the resin include interpolymers, hydrogenated aromatic vinyl/conjugated diene random copolymers, hydrogenated aromatic vinyl/conjugated diene block copolymers, and unsaturated olefin copolymers obtained by copolymerizing at least ethylene, an aromatic vinyl, and an unconjugated polyene. The resin pellets prepared by the process are superior in nontackiness to conventional pellets of an olefin copolymer rubber, etc. and are excellent in appearance and handleability.

Description

Has good inviscid resin and preparation method thereof

Technical field

The present invention relates to resin particle, particularly have soft (flexibility) resin particle of good non-sticky and outward appearance, also relate to the preparation method of these resins.

Background technology

Resin, for example soft resin as olefin-based copolymer rubber, comprises ethylene-propylene copolymer rubber, hydrogenated styrene-butadiene copolymer rubber etc., sells with bulk form such as big packet form usually.

Yet there is following defective in this block olefin-based copolymer rubber: more complicated when storage site is taken out, with its transmit, supply be shaped and procedure of processing in use equipment the time also very complicated, and their poor performance of weighing.

Therefore, if olefin-based copolymer rubber can be sold with particle form, just can avoid above-mentioned defective, a major advantage is provided simultaneously, promptly can prepare blended rubber by the forcing machine of particulate olefin-based copolymer rubber and additive directly being supplied with high efficiency, replace low mixing tank such as the Banbury mixer of production efficiency commonly used, the latter is used to mediate normally used other additives of filler, tenderizer, vulcanizing agent and olefin-based copolymer rubber.

Yet, even such olefin-based copolymer rubber granulation also can be bonded to piece owing to the viscosity of olefin copolymer resin itself between the shelf lives, thus the advantage of forfeiture granulation.

For reducing the surface viscosity of this class olefin-based copolymer rubber grain, this area once proposed many methods.For example, known have: in the method [Japanese Patent Application clear-48 (1973)-47934] of rubber particle surface coating silicone oil, and be coated with spray inorganic powder such as talcum, silicon-dioxide and antisticking agents such as lime carbonate or polyethylene powders, make powder-stuck at the particle surface that easily is viscosity.

Yet the shortcoming that is coated with the method for rubber particle surface with silicone oil is can not reach enough effects to strong sticky particle.In a kind of method in back, inorganic materials such as talcum or silicon-dioxide can not be compatible with olefin-based copolymer rubber, therefore when these powder-stucks, often the performance on the end-use produced detrimentally affect.And for effectively preventing particle bond, this method need add the antisticking agent of percentum to percent tens of particle weight, and Duo powder can produce detrimentally affect to the performance of the olefin-based copolymer rubber of need processing like this.For example, be coated with when spreading polyethylene powders on the olefin-based copolymer rubber grain, the polyethylene mould inhibitor that is glued has in a large number damaged the rubber performance of sulfurized olefin-based copolymer rubber.Another shortcoming of this method is can destroy particle appearance and cause processing difficulties at the powder fine hair that particle surface produces.

The applicant once proposed the effective counter measure of rubber grain agglutinating, promptly with higher fatty acid and/or its salt coating rubber grain (Japanese Patent Application clear-56 (1981)-136347).According to the method, can prevent the viscosity of rubber grain, not damage rubber performance substantially.

Yet, the applicant finds, method described in the above-mentioned application can not make higher fatty acid and/or its salt stably be adhered to rubber grain with q.s, because higher fatty acid and/or its salt and rubber are simple blended, between the shelf lives or transmit, weigh and other still can produce caking in handling.

After further fully studying, the applicant proposes a kind of method that prevents that rubber grain from luming between the shelf lives, in this method, the olefin-based copolymer rubber grain mixes in the presence of the monohydroxy-alcohol that 1-4 carbon atom arranged with the fine powder of the higher fatty acid that 12-30 carbon atom arranged and/or its salt, makes low bala gutta particle (Japanese Patent Application flat-4 (1992)-1011).Obtain rubber grain with higher fatty acid and/or the coating of its salt according to the method after filling and transportation, in addition with 25 kilograms granule packaging in a bag, these bags pile up 10 layers and left standstill 1 month, do not cause caking.Yet in this method, the powder fine hair on the particle surface can cause some troubles in the processing.

Recently, the demand with good non-sticky and outward appearance and easy-to-handle resin particle method being compared in preparation with the resin particle of common olefin-based copolymer rubber constantly increases.

The present invention is intended to solve these problems of the prior art, provides to compare with the resin particle of common olefin-based copolymer rubber to have good non-sticky and outward appearance and easy-to-handle resin particle.

Summary of the invention

The present invention has good inviscid resin particle and comprises (A) at least a resin that is selected from following (i)-(iv), 23 ℃ of tensile moduluses (YM:ATM D-658) of these resins are smaller or equal to 1600MPa, it is 0.5-100 that described particle surface covers (B) at least a 25 ℃ of dynamic viscosities, 000cSt and 25 ℃ of surface tension are the liquid of 10-50dyne/cm and the fine powder of (C) being made up of smaller or equal at least a organic fine powder or the fine silica end of 50 μ m mean particle size

(i) the random substantially polymers (interpolymer) that closes comprises:

(1) 1-99% (mole) is derived from following monomeric polymerized unit;

(a) at least a aromatic vinyl or vinylidene monomer,

(b) at least a have aliphatic series or cycloaliphatic vinyl or a vinylidene monomer that is obstructed, or

(c) at least a aromatic vinyl or vinylidene monomer and at least a mixture that the aliphatic vinyl that is obstructed or cycloaliphatic vinyl or vinylidene monomer arranged and

(2) polymerized unit of the alpha-olefin that is derived from an ethene and/or at least a 3-20 of a having carbon atom of 99-1% (mole),

(ii) hydrogenation random copolymers, it is the hydrogenated products by the multipolymer of random copolymerization aromatic vinyl compound and conjugated diolefine acquisition, wherein, the hydrogenation of structural unit that is derived from the structural unit of conjugated diolefine and/or is derived from aromatic vinyl compound is than for more than or equal to 90%;

(iii) hydrogenated block copolymer, it is the hydrogenated products by the multipolymer of block copolymerization aromatic vinyl compound and conjugated diolefine acquisition, wherein, the hydrogenation of structural unit that is derived from the structural unit of conjugated diolefine and/or is derived from aromatic vinyl compound is than for more than or equal to 90%;

(iv) unsaturated olefin base co-polymer, it is to have the alpha-olefin of 3-20 carbon atom to make by copolymerization (a) ethene, (b) aromatic vinyl compound, (c) unconjugated polyene and non-essential (d), wherein, the structural unit content that is derived from (a) ethene be derived from the ratio ((a)/(d)) of structural unit content of alpha-olefin that (d) have 3-20 carbon atom in 100/0 to 60/40 scope, iodine number is in the scope of 0.5-50.

The method that the present invention's preparation has good inviscid resin particle comprises: with (B) at least a 25 ℃ of dynamic viscosities is 0.5-100,000cSt and 25 ℃ of surface tension are the liquid of 10-50dyne/cm and the fine powder of (C) being made up of smaller or equal at least a organic fine powder or the fine silica end of 50 μ m mean particle size, cover (A) at least a particle surface that is selected from the resin of above-mentioned (i)-(iv), 23 ℃ of tensile moduluses (YM:ATM D-658) of these resins are smaller or equal to 1600MPa.

The polymers (i) that closes that uses better is the random substantially polymers that closes, and comprises 1-99% (mole) and is derived from the polymerized unit of at least a aromatic vinyl or vinylidene monomer and the alpha-olefin that 99-1% (mole) is derived from least a 3-20 of a having carbon atom.Wherein, be more preferably basic random copolymers, comprise 1-99% (mole) and be derived from the polymerized unit that cinnamic polymerized unit and 99-1% (mole) are derived from the alpha-olefin of at least a 3-10 of a having carbon atom.

As closing polymers (i), better also use:

Comprise 1-65% (mole) and be derived from the false random polymers that closes that cinnamic polymerized unit and 99-35% (mole) are derived from the polymerized unit of ethene, or

Comprise 1-65% (mole) and be derived from the false random polymers that closes of polymerized unit that cinnamic polymerized unit and 99-35% (mole) are derived from the alpha-olefin of ethene and a kind of 3-20 of having carbon atom.

At this, " false random " closes polymers refers to not have vinylidene monomer in its molecular structure homopolymer fragment, described in Japanese Patent Application flat-7 (1995)-070223.That is, close in the polymers in that vacation is random, do not insert the unit to head or at head between the vinylidene monomer tail at head.

In resin (A) is 100% (weight), and resin (A) can comprise the unsaturated carboxylic acid or derivatives thereof of 0.01-30% (weight).

As liquid (B), better be silicoorganic compound, be more preferably dimethyl polysiloxane.

Fine powder (C) better is the organic radical fine powder that comprises higher fatty acid or advanced higher fatty acid derivative.Wherein, better be stearic acid, erucic acid, oleic acid, methylene-succinic acid, montanic acid and their metal-salt, acid amides and ester.

The best mode that carries out an invention

Below, will describe the present invention in detail and have good inviscid resin particle and preparation method thereof.

The present invention has in good inviscid resin particle, the particle surface of specific resin (A) has covered (coating) at least a liquid (B) and fine powder (C), liquid (B) has specific viscosity and surface tension at 25 ℃, and fine powder (C) is made of at least a organic fine powder or fine silica end with certain mean particle size.

Therefore, resin particle of the present invention can be by preparing with at least a liquid (B) with by at least a particle surface with organic fine powder of certain mean particle size or fine powder (C) covering (coating) specific resin (A) that the fine silica end constitutes.

At first describe and be used to have good non-viscous resin particulate resin (A), liquid (B) and fine powder (C).

Resin (A)

The 23 ℃ of tensile moduluses (YM:ASTM D-658) that are used for resin of the present invention (A) are generally 1-1600MPa for smaller or equal to 1600MPa, are preferably 1-1200MPa.As having of resin (A): close polymers (i), hydrogenation random copolymers (ii), hydrogenated block copolymer (iii) with the unsaturated olefin base co-polymer (iv).These resins (A) can use separately, or two or more are used in combination.As two or more combination, the example that can mention is as follows:

(1) close polymers (i) and hydrogenation random copolymers mixture (ii),

(2) close polymers (i) and hydrogenated block copolymer mixture (iii),

(3) close polymers (i) and unsaturated olefin base co-polymer mixture (iv),

(4) the hydrogenation random copolymers (ii) with hydrogenated block copolymer mixture (iii),

(5) the hydrogenation random copolymers (ii) with unsaturated olefin base co-polymer mixture (iv),

(6) (iii) unsaturated olefin base co-polymer mixture (iv) of hydrogenated block copolymer,

(7) close polymers (i), hydrogenation random copolymers (ii) with hydrogenated block copolymer mixture (iii),

(8) close polymers (i), hydrogenation random copolymers (ii) with unsaturated olefin base co-polymer mixture (iv),

(9) close polymers (i), hydrogenated block copolymer (iii) with unsaturated olefin base co-polymer mixture (iv).

(closing polymers (i))

Being used for the polymers (i) that closes of the present invention is the random substantially polymers that closes, and comprises:

(1) 1-99% (mole) is derived from following monomeric polymerized unit;

(a) at least a aromatic vinyl or vinylidene monomer,

(b) at least a aliphatic vinyl monomer that is obstructed, the cycloaliphatic vinyl monomer that is obstructed, the aliphatic vinylidene that is obstructed or the alicyclic vinylidene monomer that is obstructed, or

(c) mixture of at least a aromatic vinyl monomer and at least a aliphatic vinyl monomer that is obstructed, the cycloaliphatic vinyl monomer that is obstructed, the aliphatic vinylidene that is obstructed or the alicyclic vinylidene monomer that is obstructed and

(2) polymerized unit of the alpha-olefin that 3-20 carbon atom arranged that is derived from ethene and/or at least a type of 99-1% (mole).

Term " closes polymers " and refers to multipolymer by at least two kinds of different monomers preparations of polymerization and forms and close polymers as used herein.

Term " multipolymer " refers to form multipolymer by the polymkeric substance of at least two kinds of different monomers preparations of polymerization as used herein.

The random substantially term " random substantially " that uses in the polymers that closes at the alicyclic vinylidene monomer that comprises alpha-olefin, aromatic vinyl monomer, aromatics vinylidene monomer, the aliphatic vinyl monomer that is obstructed, the cycloaliphatic vinyl monomer that is obstructed, the aliphatic vinylidene that is obstructed or be obstructed, the monomer distribution that finger closes polymers, according to " POLYMER SEQUENCE DETERMINATION, Carbon- ¹³NMR Method ", pp.71-78 by J.C.Randall, 1977, Academic Press described in the New York, can be described as " Bernoulli Jacob's statistical model " or " one-level or secondary Markovian statistical model ".

Comprise ethene or the alpha-olefin of 3-20 carbon atom is arranged and the aromatic vinyl that exists with block form in the polymers is closed in aromatic vinyl or vinylidene monomer random substantially or the content of vinylidene monomer better is no more than 15% of total amount, this monomer have unit more than 3 (for example, styrene monomer have 4 or more be derived from cinnamic unit).Better, close the characteristic that polymers does not have high degree of isotacticity or degree of syndiotacticity.This means the C-that closes polymers random substantially ¹³In the NMR spectrum, should not surpass 75% of the total peak area of main chain methylene radical and methine carbon corresponding to the peak area of main chain methylene radical with meso diad order or racemize diad order and methine carbon.

The polymkeric substance that is fit to preparation resin particle of the present invention includes but not limited to: by the polymers that closes of one or more alpha-olefins of polymerization and one or more aromatic vinyls or vinylidene monomer and/or one or more aliphatic series of being obstructed or cycloaliphatic vinyl or vinylidene monomer acquisition.

Have as the example of alpha-olefin preferably: contain 3-20 carbon atom, better 3-12 carbon atom, be more preferably the alpha-olefin of 3-8 carbon atom.Wherein best is propylene, 1-butylene, 4-methyl-1-pentene, 1-hexene and 1-octene.These alpha-olefins do not contain aryl.Good especially is ethene.

Be used to prepare the monomer that the suitable example of aromatic vinyl that the present invention closes polymers (i) or vinylidene monomer has following formula to represent: In this formula, R ¹Being the alkyl that is selected from hydrogen atom or contains 1-4 carbon atom, better is hydrogen atom or methyl.

R ²Also being the alkyl of a hydrogen atom or 1-4 carbon atom, better is hydrogen atom or methyl and and R ¹Irrelevant.

Ar be phenyl or by 1-5 halogen atom, contain the alkyl of 1-4 carbon atom and contain the substituted-phenyl that the haloalkyl of 1-4 carbon atom replaces.

Letter n is the integer of 0-4, better is the integer of 0-2, preferably 0.

The monomeric object lesson of aromatic monovinyl or monovinylidene comprises: vinylbenzene, Vinyl toluene, alpha-methyl styrene, t-butyl styrene, chloro-styrene etc. also comprise their all isomer.Better aromatic monovinyl or monovinylidene monomer comprise the derivative that vinylbenzene and low alkyl group or halogen replace.Monomer is the derivative that vinylbenzene, alpha-methyl styrene and low alkyl group (1-4 carbon atom alkyl) or phenyl replace preferably, for example adjacent,, p-methylstyrene, cyclosubstituted vinylbenzene, to Vinyl toluene and their mixture.Best aromatic monovinyl monomer is a vinylbenzene.

Term " aliphatic series of being obstructed or cycloaliphatic vinyl or vinylidene compound " refers to polymerisable vinyl of addition or vinylidene monomer on corresponding to the compound of following formula:

In this formula, A ¹Be to contain to be less than or to equal 20 carbon atoms and spatial volume bigger aliphatic series or alicyclic substituting group.

R ¹Being the alkyl that is selected from hydrogen atom or 1-4 carbon atom, better is hydrogen atom or methyl.

R ²Being the alkyl of a hydrogen atom or 1-4 carbon atom, better is hydrogen atom or methyl, and and R ¹Irrelevant.

R ¹And A ¹Can form ring together.

Term " spatial volume is bigger " refers to have aliphatic series or alicyclic substituent monomer when using the standard Ziegler-Natta catalyst, can not carry out polyaddition reaction with the speed that is equivalent to ethylene polymerization.

Aliphatic series of being obstructed preferably or cycloaliphatic vinyl or vinylidene compound be one of them have the carbon atom of unsaturated ethylene linkage have uncle's substituting group or season substituent monomer.Substituent example comprises alicyclic group such as cyclohexyl, cyclohexenyl and cyclooctene base, or the derivative of their cycloalkyl or aryl replacement.Aliphatic series of better being obstructed or cycloaliphatic vinyl or vinylidene compound are the cyclosubstituted derivatives of isomerization vinyl of the cyclohexyl of various hexanaphthenes and replacement, and 5-vinylidene-2-norbornylene.Preferably 1-, 3-and 4 vinyl cyclohexene.

The polymers that closes by polymerising ethylene and/or one or more alpha-olefins and one or more aromatic vinyls or vinylidene monomer and/or one or more aliphatic series of being obstructed or cycloaliphatic vinyl or vinylidene monomer acquisition is a kind of unregulated polymer substantially.The polymers that closes like this comprises 1-99% (mole) usually, better be 1-65% (mole), one or more aromatic vinyls or vinylidene monomer and/or the aliphatic series of being obstructed or cycloaliphatic vinyl or the vinylidene monomer of better 5-50% (mole), and 99-1% (mole), better be 35-99% (mole), be more preferably 50-95%'s (mole) and the alpha-olefin that contains 3-20 carbon atom or their mixture.

The number-average molecular weight (Mn) of closing polymers is generally more than or equal to 10,000, is preferably 20,000-1,000,000, more preferably 50,000-500,000.

Simultaneously, preparation is random substantially close polymers during, heating down, the homopolymerization of aromatic vinyl or vinylidene monomer can produce a certain amount of atactic aromatic vinyl or vinylidene homopolymer.The existence of aromatic vinyl or vinylidene homopolymer is unwanted for the object of the invention.If desired, can from close polymers, isolate aromatic vinyl or vinylidene homopolymer, for example use the non-solvent that closes polymers, aromatic vinyl and vinylidene homopolymer, selective precipitation from solution by extractive technique.Considering from the object of the invention, is benchmark to close the polymers gross weight, and the amount of remaining aromatic vinyl or vinylidene homopolymer is better smaller or equal to 20% (weight), better smaller or equal to 15% (weight).

According to the U.S. Patent application 07/545 of people such as James C.Steven in application on July 3 nineteen ninety, 403 (corresponding to EP-A-0,416,815), in the U.S. Patent application 08/469 of application on June 6 nineteen ninety-five, 828 and the United States Patent (USP) 5 of authorizing, method described in 703,187 can prepare the random substantially polymers that closes.The content of these United States Patent (USP) mandates is incorporated herein by reference.The better polymerization reaction conditions is: pressure: normal pressure to 3000 normal atmosphere, temperature :-30 ℃ to 200 ℃.When under being higher than each monomer autopolymerization temperature of reaction, carrying out polymerization and removing unreacted monomer, make some homopolymer products by Raolical polymerizable.

The example that preparation is used for random substantially better catalyst of closing polymers of the present invention and method is disclosed in the U.S. Patent application 07/545,403 (corresponding to EP-A-416,815) of application on July 3 nineteen ninety; The U.S. Patent application 07/702,475 (corresponding to EP-A-514,828) of application on May 20th, 1991; The U.S. Patent application 07/876,268 (corresponding to EP-A-520,732) of application on May 1st, 1992; The U.S. Patent application 08/241,523 of application on May 12nd, 1994 (authorizing United States Patent (USP) 5,470,993); With United States Patent (USP) 5,005,438; 5,057,475; 5,096,867; 5,064,802; 5,132,380; 5,189,192; 5,321,106; 5,347,024; 5,350,723; 5,374,696; 5,399,635 and 5,556,928.All the elements of these documents are incorporated herein by reference.

Being used for random substantially alpha-olefin/aromatic vinyl of the present invention or vinylidene closes polymers and can also pass through WO95/32095 (people such as John C.Bradfute) (W.R.Grace ﹠amp; Co) described method, (P.25 (September, 1992) described method prepares WO94/00500 (R.B.Pannell) for Exxon Chemical Patent, Inc.) described method and " plastics technology ".All the elements of these documents are incorporated herein by reference.

Also have preferably: as the United States Patent (USP) of applying on September 4th, 1996 by people such as Francis J.Timmers 08/708,809 (United States Patent (USP)s 5,879,149) the random substantially polymers that closes that comprises at least a alpha-olefin/aromatic vinyl/aromatics vinylidene/alpha-olefin tetramer described in.These close polymers and have other signals than big three dual intensities of peak value peak noise.These signals appear in the chemical shift range of 43.75-44.25ppm and 38.0-38.5ppm.44.1,43.9 and 38.2ppm observe especially the peak of point.In proton N MR test, the signal in the chemical shift range of 43.75-44.25ppm is represented methine carbon, and the signal in the chemical shift range of 38.0-38.5ppm is represented mesomethylene carbon.

Can be used for the vacation-random polymers that closes that comprises aliphatic α-alkene and aromatic monovinyl or vinylidene compound of the present invention and be disclosed in the United States Patent (USP) of applying for July 3 nineteen ninety 07/545,403 (corresponding to EP-A-0416815).

These close polymers (i) can if desired, at the catalyzer that is expressed from the next, better be the polyreaction preparation under co-catalyst exists by under-30 ℃ to 250 ℃ temperature. Wherein, each Cp is the cyclopentadienyl that π is bonded to the replacement of M independently of one another, E is carbon atom or Siliciumatom, M is the metal of period of element Table IV family, better be Zr or Hf, Zr preferably, R is hydrogen atom or alkyl independently of one another, have 30 or less than 30, be preferably 1-20, more preferably the silicon alkyl or the alkyl silyl of 1-10 carbon atom or Siliciumatom, R ' is hydrogen atom independently of one another, halogen atom or have 30 or less than 30 is preferably 1-20, the alkyl of 1-10 carbon atom or Siliciumatom more preferably,-oxyl, silicon alkyl or alkyl silyl, or two R ' bases form C together _1-10The 1,3-butadiene that alkyl replaces, m is 1 or 2.The group that has following formula to represent as the cyclopentadienyl of best replacement:

Wherein, R is hydrogen atom independently of one another or has 30 or less than 30, is preferably 1-20, more preferably alkyl,-oxyl, silicon alkyl or the alkyl silyl of 1-10 carbon atom or Siliciumatom, or two R bases form the divalent derivative of these groups together.Preferably, R is hydrogen atom, methyl, ethyl, propyl group, butyl, amyl group, hexyl, benzyl, phenyl or silyl independently, comprise the isomer that they are all, or when possible () two R groups form condensed ring together, as indenyl, fluorenyl, tetrahydro indenyl, tetrahydrofluorenyl or octahydrofluorenyl.

As having of the good especially example of catalyzer:

Racemize-dichloride (dimethylsilane two bases)-two-(2-methyl-4-phenyl indenyl) zirconium (racemic-(dimethylsilanediyl)-bi-(2-methyl-4-phenylindenyl) zirconiumdichloride),

Racemize-1,4-phenylbenzene-1,3-butadiene (dimethylsilane two bases)-two-(2-methyl-4-phenyl indenyl) zirconium,

Racemize-two C _1-4Alkyl (dimethylsilane two bases)-two-(2-methyl-4-phenyl indenyl) zirconium,

Racemize-two C _1-4Alcohol (dimethylsilane two bases)-two-(2-methyl-4-phenyl indenyl) zirconium, and their combination.

Catalyzer as specific titanium base confined configuration has following material: and dimethyl [N-(1, the 1-dimethyl ethyl)-1,1-dimethyl-1-[(1,2,3,4,5-η)-1,5,6,7-tetrahydrochysene-s-indacen-1-yl] silane amination (2-)-N] titanium;

Dimethyl (1-indenyl) (tert-butylamides base) dimethylsilane titanium;

Dimethyl ((the 3-tertiary butyl) (1,2,3,4,5-η)-1-indenyl) (tert-butylamides base) dimethylsilane titanium;

Dimethyl (3-sec.-propyl) (1,2,3,4,5-η)-1-indenyl) (tert-butylamides base) dimethylsilane titanium; And their combination.

Other preparations can be used for method of closing polymers of the present invention and are disclosed in: Longo and Grassi (Macromol.Chem., Vol.191, pp.2378-2396 (1990)) and people (Journal of AppliedPolymer Science such as D ' Anniello, Vol.58, pp.1701-1706 (1995)), wherein, use Jia base An Ji oxane (methylaminooxane) (MAO) and tri-chlorination cyclopentadienyltitanium (CpTiCl ₃) catalyst based, the preparation ethylene-styrene copolymer.Xu and Lin (Polymer preprint, Am.Chem.Soc., Div.Polym.Chem.) Vol.35, pp.686-687 (1994) uses MgCl ₂/ TiCl ₄/ NdCl ₃/ Al (iBu) ₃Catalyzer prepares the random copolymers of vinylbenzene and propylene.Also have, people such as Lu (Journal of Applied Polymer Science, Vol.53, pp.1453-1460 (1994)) have reported use TiCl ₄/ NdCl ₃/ MgCl ₂/ Al (Et) ₃Catalyzer carries out ethene and cinnamic copolyreaction.

Sernets and Mulhaupt (Macromol Chem.Phy., v.197, pp.1071-1083,1997) has discussed use dimethyl-silicon (tetramethyl-ring pentadiene) (the N-tertiary butyl) TiCl ₂/ methylaluminoxane during as Ziegler-Natta catalyst polymeric reaction condition to the influence of vinylbenzene and ethylene copolymer reaction.

Arai, Toshiaki and Suzuki (Polymer Preprint s, Am.Chem.Soc., Div.Polym.Chem.Vol.38, pp.349-350,1997) and United States Patent (USP) 5,652,315 (Mitsui ToatsuChemical Co. Ltd.) has described the ethylene-styrene copolymer that uses the preparation of bridge type metalloscene catalyst.

At United States Patent (USP) 5,244,996 (Mitsui Petrochemical Industries Co., Ltd.) and United States Patent (USP) 5,652,315 (Mitsui Petrochemical Industries Co., Ltd.) and open DE19711339A1 of German Patent and United States Patent (USP) 5, the method of closing polymers that preparation is made up of alpha-olefin/aromatic vinyl monomer (for example, propylene-styrene and butylene-styrene) has been described among 883,213 (the Denki Kagaku Kogyo K.K.).

The preparation of describing in above-mentioned document is closed the method for polymers component and is quoted as a reference by the present invention at this.

By Aria, people such as Tooru in March, 1998 at Polymer Preprints, Vol.39, No.1, disclosed ethene-styrene random multipolymer also can be used as integral part of the present invention.

U.S. Patent application 07/545 in application on July 3 nineteen ninety, 403 (European patent communique No.0416815), U.S. Patent application 07/547 in application on July 3 nineteen ninety, 718 (European patent communique No.468651), U.S. Patent application 702475 (European patent communique No.514828) in application on May 20th, 1991, U.S. Patent application 876268 (European patent communique No.520732) in application on May 1st, 1992, U.S. Patent application 8003 (United States Patent (USP) 5 in application on January 21st, 1993,374,696), U.S. Patent application 82197 (corresponding to WO95/00526) in application on June 24th, 1993, and United States Patent (USP) 5,005,438,5,057,475,5,096,867,5,064,802,5,132380 and 5, disclose the suitable example for preparing the Catalyst And Method that is applicable to vacation-unregulated polymer of the present invention in 189,192, these documents are incorporated herein by reference.

Be used for the polymers (i) that closes of the present invention and can carry out graft modification with free radical polymerizable monomer with active polar group.To close polymers weight before the graft modification is that 100% (weight) is benchmark, and the amount of monomer of closing radical polymerization in the polymers that is grafted on modification should be in 0.01-30% (weight) scope, and more preferably 0.01-10% (weight) is preferably 0.1-2% (weight).

Be used for the free yl polymerizating monomer with active polar group of the present invention and be containing the monomer of the two keys of at least one radical polymerization, and be at least aly to be selected from hydroxyl ethylene linkage unsaturated compound, to contain amino ethylene linkage unsaturated compound, the ethylene linkage unsaturated compound that contains epoxy group(ing), aromatic vinyl compound, unsaturated carboxylic acid and their derivative, vinyl acetate compound, to contain nitro unsaturated compound and Ethylene Dichloride at its molecule.

Object lesson as the ethylene linkage unsaturated compound of hydroxyl has:

(methyl) acrylate is as (methyl) Hydroxyethyl Acrylate, (methyl) vinylformic acid 2-hydroxy propyl ester, (methyl) vinylformic acid 3-hydroxy propyl ester, (methyl) vinylformic acid 2-hydroxyl-3-phenoxy group propyl ester, (methyl) vinylformic acid 3-chloro-2-hydroxy propyl ester, single (methyl) vinylformic acid glycol ester, single (methyl) vinylformic acid pentaerythritol ester, TriMethylolPropane(TMP) list (methyl) acrylate, tetra methylol ethane list (methyl) acrylate, single (methyl) vinylformic acid butanediol ester, single (methyl) vinylformic acid polyethylene glycol ester and vinylformic acid 2-(6-hydroxyl hexylyloxy) ethyl ester (2-(6-hydroxyhexanolyoxy) ethyl acrylate);

10-undecene-1-alcohol, 1-octene-3-alcohol, 2-methyl alcohol bornylane (2-methanolnorbornane), hydroxy styrenes, hydroxyethyl vinyl ether, hydroxybutyl vinyl ether, N hydroxymethyl acrylamide, 2-(methyl) vinylformic acid acryloxy ethylhexyldithiophosphoric acid phosphoric acid ester, allylin, vinyl carbinol, acryloxy ethanol, 2-butylene-1,4-two pure and mild glycerine list alcohol.

Above-mentioned amino-contained ethylene linkage unsaturated compound is that two keys of an ethylene linkage and amino compound are arranged, and this compounds includes the vinyl monomer of the substituted-amino that at least one amino or following formula represent:

Wherein, R ³Be hydrogen atom, methyl or ethyl, R ⁴Be that hydrogen atom, a 1-12 carbon atom are preferably the alkyl of 1-8 carbon atom or the cycloalkyl that 6-12 carbon atom is preferably 6-8 carbon atom.Alkyl or cycloalkyl can also have substituting group.

The concrete amino ethylene linkage unsaturated compound that contains has;

The alkyl derivative of acrylic or methacrylic acid, for example (methyl) acrylic-amino ethyl ester, (methyl) vinylformic acid propyl group amino ethyl ester, dimethylaminoethyl methacrylate, (methyl) acrylic-amino propyl ester, methacrylic acid phenyl amino ethyl ester and methacrylic acid cyclohexyl amino ethyl ester;

Vinyl sulfonamide derivatives, for example N vinyl diethylamine and N-ethanoyl vinyl amine;

The allyl amine derivative, for example allyl amine, Methacrylamide, N methacrylamide, N,N-DMAA and N, N-dimethyl amido propyl group acrylamide;

Acrylamide derivative, for example acrylamide and N methacrylamide;

Amido vinylbenzene is as to amido vinylbenzene;

And 6-amido hexyl succinimide, 2-amido ethyl succinimide etc.

The acyl group unsaturated compound that contains epoxide group is the monomer that at least one polymerizable unsaturated bond and epoxy group(ing) are arranged in its molecule, and it is as follows that this class contains the object lesson of acyl group unsaturated compound of epoxide group:

Glycidyl acrylate and glycidyl methacrylate;

The monoalkyl glycidyl ester of dicarboxylic acid and two alkyl glycidyl ester are (under single glycidyl ester situation, alkyl has 1-12 carbon atom), the for example single glycidyl ester and the 2-glycidyl ester of toxilic acid, the single glycidyl ester and the 2-glycidyl ester of fumaric acid, the single glycidyl ester and the 2-glycidyl ester of Ba Dousuan, the single glycidyl ester and the 2-glycidyl ester of tetrahydrophthalic acid, the single glycidyl ester and the 2-glycidyl ester of methylene-succinic acid, tricarboxylic single glycidyl ester of butylene and 2-glycidyl ester, the single glycidyl ester and the 2-glycidyl ester of citraconic acid, in-suitable-two rings [2.2.1]-heptan-5-alkene-2,3-two shrink (Nadic acid ^TM) single glycidyl ester and 2-glycidyl ester, interior-suitable-two the ring [2.2.1]-heptan-5-alkene-2-methyl-2,3-dicarboxylic acid (Methylnadic acid ^TM) single glycidyl ester and the single glycidyl ester and the 2-glycidyl ester of 2-glycidyl ester and allyl group succsinic acid;

Alkyl glycidyl ester, glycidyl allyl ether, 2-methacrylic glycidyl ether, vinylbenzene-p glycidyl ether, 3 to the vinylbenzene carboxylic acid, 4-epoxy-1-butylene, 3,4-epoxy-3-methyl-1-butene, 3,4-epoxy-1-amylene, 3,4-epoxy-3-Methyl-1-pentene, 5, the single oxide compound of 6-epoxy-1-hexene and vinyl cyclohexene.

As aromatic vinyl compound, the compound that has following formula to represent: In the formula, R ⁵And R ⁶Can be identical or different, they can be hydrogen atom or the alkyl that 1-3 carbon atom arranged, and methyl, ethyl, propyl group and sec.-propyl are specifically arranged.

R ⁷Be alkyl or the halogen atom that 1-3 carbon atom arranged, methyl, ethyl, propyl group and sec.-propyl are specifically arranged, and chlorine, bromine and iodine atom.

Letter n is the integer of 0-5 normally, better is the integer of 1-5.

As this class aromatic vinyl compound, specifically have: vinylbenzene, alpha-methyl styrene, o-methyl styrene, p-methylstyrene, a vinyl toluene, chloro-styrene, m-chlorostyrene, p-chloromethyl styrene, 4-vinylpridine, 2-vinyl pyridine, 5-ethyl-2-vinyl pyridine, 2-methyl-5-vinylpyrine, 2-isopropyl pyridine, 2-vinylquinoline, 3-vinyl isoquinoline 99.9, N-vinylcarbazole and N-vinyl pyrrolidone.

As unsaturated carboxylic acid, specifically have: vinylformic acid, methacrylic acid, toxilic acid, fumaric acid, tetrahydrophthalic acid, methylene-succinic acid, citraconic acid, Ba Dousuan, iso-crotonic acid, borneol alkyl dicarboxylic aid, Nadic acid ^TM(interior, 3-dicarboxylic acid and interior-suitable-two ring [2.2.1]-hept-2-ene"s-5,6-two contract carboxylic acid) along two rings [2.2.1] heptan-5-alkene-2.

The example of olefinically unsaturated carboxylic acid derivatives has: the acyl halide of above-mentioned unsaturated carboxylic acid, amide compound, imide compound, anhydride compound and ester cpds.Specifically have: maleoyl chlorine; maleimide; maleic anhydride; itaconic anhydride; citraconic anhydride; the tetrahydrobenzene dicarboxylic acid anhydride; interior along two ring [2.2.1] hept-2-ene"s-5; 6-two shrink acid anhydrides; dimethyl maleate; dimethyl fumarate; dimethyl itaconate; the citraconic acid dimethyl ester; the tetrahydro-rutgers; interior along two ring [2.2.1] hept-2-ene"s-5,6-dimethyl dicarboxylate; the toxilic acid glycidyl ester; (methyl) Hydroxyethyl Acrylate; (methyl) vinylformic acid hydroxy propyl ester; (methyl) glycidyl acrylate; methacrylic acid amido ethyl ester and methacrylic acid amido propyl ester.

Wherein, be preferably (methyl) vinylformic acid, maleic anhydride, (methyl) Hydroxyethyl Acrylate, glycidyl methacrylate and methacrylic acid amido propyl ester.

As the vinyl ester compound, specifically have: vinyl-acetic ester, propionate, vinyl propionate, isobutyrate, new vinyl acetate acid, vinyl caproate, vinyl versatate, vinyl laurate, stearic acid vinyl ester, vinyl benzoate, p-tert-butyl benzoic acid vinyl acetate, vinyl salicylate and hexanaphthene shrink vinyl acetate.

Unsaturated compound as containing nitro specifically has: vinyl cyanide, methacrylonitrile, flumaronitrile (fumaronitrile), allyl cyanide and vinylformic acid cyanogen ethyl ester (cyanoethyl acrylate).

What polymerization was better used in the monomer of these free redical polymerizations is maleic anhydride, (methyl) vinylformic acid, (methyl) Hydroxyethyl Acrylate, (methyl) vinylformic acid 2-hydroxy propyl ester, (methyl) vinylformic acid amido ethyl ester, (methyl) vinylformic acid propyl group amido ethyl ester, (methyl) glycidyl acrylate, vinylbenzene, (methyl) methyl acrylate, (methyl) ethyl propenoate, (methyl) vinylformic acid tetrahydro furfuryl ester, (methyl) acrylamide and (methyl) vinyl cyanide.

By known graft polymerization procedure commonly used, come graft modification to close polymers by the monomer of free redical polymerization.

The example of these methods has: melting is closed polymers and is added the method that unsaturated carboxylic acid etc. carries out graft polymerization reaction therein; Be dissolved in the solvent and add the monomer of free redical polymerization therein closing polymers, thereby carry out graft polymerization reaction.

These methods are in this, if in the presence of radical initiator, carry out graft polymerization reaction, and the effectively graft polymerization of the monomer of free redical polymerization.In this case, be 100 weight parts to close polymers, the radical initiator consumption is generally the 0.001-1 weight part.

Can use organo-peroxide and azo-compound etc. as radical initiator.The object lesson of radical initiator has: benzoyl peroxide, dichlorobenzoyl peroxide, dicumyl peroxide, di-t-butyl peroxide, 2,5-dimethyl-2,5-two (peroxidation phenylformic acid) hexin-3,1,4-two (t-butyl peroxy sec.-propyl) benzene, lauroyl peroxide, t-butyl peroxy-acetate, 2,5-dimethyl-2,5-two (t-butyl peroxy) hexin-3,2,5-dimethyl-2,5-two (t-butyl peroxy) hexane, peroxidized t-butyl perbenzoate, cross the phenylacetic acid tert-butyl ester, t-butylperoxy isobutylate, cross the Zhong Xin tert-butyl acrylate, cross the PIVALIC ACID CRUDE (25) tert-butyl ester, cross PIVALIC ACID CRUDE (25) cumyl ester, cross the diethylacetic acid tert-butyl ester, Diisopropyl azodicarboxylate and dimethyl azo butyric ester.

Wherein, be preferably dialkyl peroxide, dicumyl peroxide, 2 for example, 5-dimethyl-2,5-two (t-butyl peroxy) hexin-3,2,5-dimethyl-2,5-two (t-butyl peroxy) hexane and 1,4-two (t-butyl peroxy sec.-propyl) benzene.

Temperature of reaction to the graft polymerization reaction that uses such radical initiator or the graft polymerization reaction that do not use radical initiator generally is set in 60-300 ℃, is preferably 80-230 ℃.

(the hydrogenation random copolymers (ii))

The hydrogenation random copolymers that the present invention uses (ii) is the hydrogenated products by the multipolymer of the random copolymerization acquisition of aromatic vinyl compound and conjugated diolefine, and be hydrogenation random copolymers (ii-a), the hydrogenation of component that wherein is derived from conjugated diolefine and/or is derived from aromatic vinyl compound is than more than or equal to 90%, or by obtain the hydrogenation random copolymers (ii-b) of graft modification with unsaturated carboxylic acid or derivatives thereof graft modification multipolymer (ii-a), its 23 ℃ of tensile moduluses (YM:ASTM D-658) are less than or equal to 1600Mpa, be generally 1-1600Mpa, be preferably 1-1200Mpa.

As aromatic vinyl compound, specifically have: vinylbenzene, alpha-methyl styrene, 3-vinyl toluene, p-methylstyrene, 4-propylstyrene, 4-dodecyl vinylbenzene, 4-phenylcyclohexane ethene, 2-ethyl-4-benzyl vinylbenzene, 4-(phenyl butyl) vinylbenzene, 1-vinyl naphthalene and 2-vinyl naphthalene.Wherein better be vinylbenzene.

As conjugated diolefine, divinyl, isoprene, pentadiene, 2 are specifically arranged, 3-dimethylbutadiene and their mixture.Wherein, be preferably divinyl, isoprene and divinyl and isoprene mixture.

Aromatic vinyl compound/conjugated diolefine random copolymers comprises 5-50% (weight), be preferably the structural unit that is derived from aromatic vinyl compound of 5-35% (weight), and 50-95% (weight), be preferably the structural unit that is derived from conjugated diolefine of 65-95% (weight).

Adopt ordinary method such as infrared spectrum or NMR spectrometry to be derived from the content of aromatic vinyl structural unit.

The melt flow rate (MFR) of aromatic vinyl compound/conjugated diolefine random copolymers (MFR:ASTM D1238,200 ℃, 2.16 kilogram load) was generally the 0.001-200 gram/10 minutes, was preferably 0.1-100 gram/10 minutes, and more preferably the 0.01-50 gram is/10 minutes.

Aromatic vinyl compound/conjugated diolefine random copolymers can by any oneself know ordinary method preparation.

Be used for hydrogenation random copolymers of the present invention and (ii) be above-mentionedly carrying out one of hydrogenant aromatic vinyl compound/conjugated diolefine random copolymers by the known conventional method, the hydrogenation ratio that is derived from conjugated diolefine and/or is derived from the structural unit of aromatic vinyl compound is equal to or greater than 90%.

When being derived from conjugated diolefine and/or be derived from the own hydrogenation of whole carbon-carbon double bonds of aromatic vinyl compound, its hydrogenation ratio with 100% as hydrogenation ratio.

As such hydrogenation random copolymers (ii), specifically have: hydrogenated styrene-isoprene random copolymers and hydrogenated styrene-butadiene random copolymer.

As hydrogenation random copolymers of the present invention modified hydrogenated random copolymers (ii-b) (ii) is by unsaturated carboxylic acid or derivatives thereof (below be called unsaturated carboxylic acid etc.) is grafted to the soft resin for preparing on the hydrogenation random copolymers (ii-a).

The unsaturated carboxylic acid etc. that is used to prepare modified random copolymerization thing (ii-b) is identical with the unsaturated carboxylic acid of preparation ethene improved-alpha-olefin-aromatic vinyl compound multipolymer (i-1-b) usefulness etc.

With the hydrogenation random copolymers (ii-a) before the graft modification is that 100% (weight) is as benchmark, the grafting amount of the unsaturated carboxylic acid in modified random copolymerization thing (ii-b) etc. is in 0.01-30% (weight), be preferably 0.01-10% (weight), more preferably 0.1-2% (weight).

Adopt conventional known graft polymerization procedure can finish by the graft modification to hydrogenation random copolymers (ii-a) such as unsaturated carboxylic acid.

The example of ordinary method has: fusion hydrogenation random copolymers (ii-a) also adds unsaturated carboxylic acid etc. therein and carries out the method for graft polymerization reaction and be dissolved in hydrogenation random copolymers (ii-a) in the solvent and add the method that unsaturated carboxylic acid carries out graft polymerization reaction therein.

In these methods, when in the presence of radical initiator, carrying out graft polymerization reaction, the effective grafted monomer of graft polymerization unsaturated carboxylic acid.In this case, be 100 weight parts in hydrogenation random copolymers (ii-a), the radical initiator consumption is generally the 0.001-1 weight part.

Organo-peroxide and azo-compound etc. can be used as radical initiator.Concrete radical initiator is identical with the radical initiator that is used to prepare ethene improved-alpha-olefin-aromatic vinyl compound multipolymer (i-1-b).

(hydrogenated block copolymer (iii))

Be used for hydrogenated block copolymer of the present invention and (iii) be the hydrogenated products of the multipolymer that the block copolymerization by aromatic vinyl compound and conjugated diolefine obtains, be a kind of hydrogenated block copolymer (iii-a), wherein, the hydrogenation ratio of structural unit that is derived from conjugated diolefine and/or is derived from aromatic vinyl compound is more than or equal to 90%, or modified hydride block copolymer (iii-b) by (iii) obtaining with unsaturated carboxylic acid or derivatives thereof graft modification multipolymer, its tensile modulus of 23 ℃ (YM:ASTM D-658) is less than or equal to 1600MPa, being generally 1-1600MPa, is 1200MPa preferably.

Being used for hydrogenated block copolymer of the present invention (iii) is hydrogenation aromatic vinyl compound/conjugated diene block copolymer, comprises block polymer unit (X) that is derived from aromatic vinyl compound and the block polymer unit (Y) that is derived from conjugated diolefine.

Configuration with aromatic vinyl compound/conjugated diene block copolymer of this structure can be by, X (YX) _mOr (XY) _n[wherein, n be 1 or bigger integer] expression.X (YX) preferably _n, those multipolymers of X-Y-X configuration especially, wherein, best is polystyrene-poly divinyl (or polyisoprene or polyisoprene-divinyl)-polystyrene block copolymer.

In such styryl segmented copolymer, constitute the cross-linking set of hard segmental aromatic vinyl compound block polymer unit (X), form physical crosslinking (zone) as conjugated diene rubber block polymer unit (Y).Conjugated diene rubber block polymer unit (Y) between aromatic vinyl compound block polymer unit (X) is the soft segment with caoutchouc elasticity.

Aromatic vinyl compound as forming block polymer unit (X) specifically has: vinylbenzene, alpha-methyl styrene, 3-vinyl toluene, p-methylstyrene, 4-propylstyrene, 4-dodecyl vinylbenzene, 4-phenylcyclohexane ethene, 2-ethyl-4-benzyl vinylbenzene, 4-(phenyl butyl) vinylbenzene, 1-vinyl naphthalene and 2-vinyl naphthalene.Wherein be preferably vinylbenzene.

Conjugated diolefine as forming block polymer unit (Y) specifically has: divinyl, isoprene, pentadiene, 2,3-dimethylbutadiene and their combination.Wherein, be preferably the combination of divinyl, isoprene and divinyl and isoprene.

When conjugated diene rubber block polymer unit (Y) is derived from divinyl and isoprene, should contain the unit that is derived from isoprene more than or equal to 40% (mole).

Constitute random copolymers unit or segmented copolymer unit that the so unitary conjugated diene rubber segmented copolymer of butadiene isoprene copolymer unit (Y) can be divinyl and isoprene, or the alternation copolymer unit.

Aromatic vinyl compound/conjugated diene block copolymer contains and is less than or equal to 50% (weight), is preferably the aromatic vinyl compound block polymer unit (X) of 5-22% (weight).Adopt ordinary method such as infrared spectra or the unitary content of NMR spectrometry aromatic vinyl compound.

The melt flow rate (MFR) of aromatic vinyl compound/conjugated diene block copolymer (MFR:ASTM D1283,200 ℃, 2.16 kilogram load) generally restrains/10 minutes more than or equal to 5, is preferably 5-100 gram/10 minutes.

Aromatic vinyl compound/conjugated diene block copolymer can pass through the whole bag of tricks, for example the method preparation below.

(1) use alkyl lithium compounds such as n-Butyl Lithium as initiator, aromatic vinyl compound carries out the method for successive polyreaction then with conjugated diolefine;

(2) aromatic vinyl compound and conjugated diolefine are carried out polymerization, product coupling agent link coupled method;

(3) use lithium compound as initiator, conjugated diolefine is carried out the method for successive polymerization reaction then with aromatic vinyl compound.

It (iii) is above-mentioned a kind of to aromatic vinyl compound/conjugated diene block copolymer hydrogenant by currently known methods being used for hydrogenated block copolymer of the present invention, and the hydrogenation ratio of structural unit that is derived from the conjugated diolefine structural unit and/or is derived from aromatic vinyl compound is more than or equal to 90%.

When conjugated diene rubber segmented copolymer unit (Y) and/or whole carbon-carbon double bonds of being derived from the aromatic vinyl compound structural unit hydrogenation, hydrogenation ratio is 100%, as hydrogenation ratio.

As such hydrogenated block copolymer (iii), specifically have: hydrogenated styrene-isoprene block copolymer (SEP), hydrogenated styrene-isoprene-styrene block copolymer (SEPS; Polystyrene-poly ethylene/propene-polystyrene block copolymer), hydrogenated styrene-butadiene block copolymer (SEB), hydrogenated styrene-butadiene-styrene block copolymers (SEBS; Polystyrene-poly ethylene/butylene-polystyrene block copolymer) etc., more particularly: HYBRAR (Kuraray Co., Ltd. product), Kraton (Shell Chemical Co., Ltd. trade(brand)name), Carriflex TR (Shell Chemical Co., Ltd. trade(brand)name), Sorprene (Phillip Petroleum Co., Ltd. product), Uroprene SOLT (Anicci Corp. product), Toughprene (Asahi Kasei Co., Ltd. product), Sorprene-T (Nihon Elastomer co. product), JSRTR (Nihon synthetic Rubber Co., Ltd. product), Charged STR (DerkiKagaku Kogyo K.K. product), Quintac (Nihon Zeon Co., Ltd. product), Kraton G (ShellChemical Co., trade(brand)name) and Toughtek (Asahi Kasei Co., Ltd. product) (all being trade(brand)name) Ltd..

Among the present invention, the hydrogenated block copolymer of use (iii) better is SEBS or SEPS, and the both has the better unit that is derived from aromatic vinyl compound that is less than or equal to 22% (weight), and its melt flow rate (MFR) restrains/10 minutes more than or equal to 5.

As hydrogenated block copolymer of the present invention modified hydride block copolymer (iii-b) (iii) is by unsaturated carboxylic acid or derivatives thereof (below be called unsaturated carboxylic acid etc.) is grafted on the soft resin that hydrogenated block copolymer (iii-a) is gone up preparation.

Unsaturated carboxylic acid that is used to prepare modified block copolymer (iii-b) etc. is identical with unsaturated carboxylic acid that is used to prepare ethene improved-alpha-olefin-aromatic vinyl compound multipolymer (i-1-b) etc.

With the hydrogenated block copolymer before the graft modification (iii-a) is that 100% (weight) is as benchmark, the grafting amount of the unsaturated carboxylic acid in modified block copolymer (iii-b) etc. is in 0.01-30% (weight) scope, be preferably 0.01-10% (weight), more preferably 0.1-2% (weight).

Adopt conventional known graft polymerization procedure can finish by the graft modification to hydrogenated block copolymer (iii-a) such as unsaturated carboxylic acid.

The example of ordinary method has: fusion hydrogenated block copolymer (iii-a) also adds unsaturated carboxylic acid etc. therein and carries out the method for graft polymerization reaction and be dissolved in hydrogenated block copolymer (iii-a) in the solvent and add the method that unsaturated carboxylic acid etc. carries out graft polymerization reaction therein.

In these methods, when in the presence of radical initiator, carrying out graft polymerization reaction, the effective grafted monomer of graft polymerization unsaturated carboxylic acid.In this case, be 100 weight parts in hydrogenated block copolymer (iii-a), the radical initiator consumption is generally the 0.001-1 weight part.

(the unsaturated olefin base co-polymer (iv))

Being used for unsaturated olefin base co-polymer of the present invention (iv) can be by copolymerization (a) ethene, (b) aromatic vinyl compound, (c) unconjugated polyene and non-essential (d) have the alpha-olefin of 3-20 carbon atom to obtain, wherein, the structural unit content that is derived from (a) ethene be derived from (d) and the molar ratio ((a)/(d)) of structural unit content of alpha-olefin of 3-20 carbon atom arranged in 100/0 to 60/40 scope, iodine number is in the 0.5-50 scope, can be that the unsaturated olefin base co-polymer is (iv) or with unsaturated carboxylic acid or derivatives thereof graft modification multipolymer modification unsaturated olefin base co-polymer (iv-b) (iv); 23 ℃ of tensile moduluses (YM:ATM D-658) are less than or equal to 1600MPa, are generally 1-1600Mpa, are preferably 1-1200MPa.

With the concrete aromatic vinyl compound (b) of ethene (a) copolymerization, can use the compound of following general formula (I) expression:

Wherein, R ¹, R ²And R ³Each other can be identical or different, each is hydrogen atom or the alkyl of 1-8 carbon atom is arranged naturally, better is hydrogen atom or the alkyl that 1-3 carbon atom arranged.

Letter n is the integer of 0-5, is preferably 0-3.

As aromatic vinyl compound (b), specifically have:

Vinylbenzene; Monoalkyl or polyalkylbenzene ethene, for example o-methyl styrene, a vinyl toluene, p-methylstyrene, neighbour, right-dimethyl styrene, adjacent ethyl styrene, an ethyl styrene and to ethyl styrene;

The styrene derivatives that contains functional group, for example methoxy styrene, phenetole ethene, vinyl benzoic acid, vinyl benzoic acid methyl esters, vinyl acetate base benzyl ester, hydroxy styrenes, neighbour-chloro-styrene, right-chloro-styrene and Vinylstyrene;

3-phenyl propylene, 4-phenyl butylene, alpha-methyl styrene etc.These aromatic vinyl compounds (b) can use separately, or two or more are used in combination.

As non-conjugated two polyenoid (c), specifically have: diolefin for example 1,4-pentadiene, 1,4-hexadiene, 4-methyl isophthalic acid, 5-heptadiene, 5-methylene-2-norbornene, 5-ethylidene-2-norbornene, 5-sec.-propyl-2-norbornylene, 2,5-norbornadiene, 1,6-cyclooctadiene, 2-ethylidene-2,5-norbornadiene, 2-propylidene-2,5-norbornadiene, cyclopentadiene, 1,6-octadiene, 1,7-octadiene and three cyclopentadiene; Non-conjugated triolefin and tetraene that a 5-norbornylene-2-base is arranged in the non-conjugated triolefin of a vinyl and tetraene and the molecule are arranged in the molecule.

The total number of carbon atoms in each molecule of non-conjugated triolefin or tetraene (the carbon atom mean number under non-conjugated triolefin of two or more differences or the tetraene situation) is had no particular limits, still, be preferably 9-30, more preferably 10-25 is preferably 10-22 carbon atom.Carbonatoms takes advantage during in the processing of implementing to purify etc. at the non-conjugated triolefin of above-mentioned scope or tetraene.

At this, " triolefin " refers to have the hydrocarbon compound of three carbon-carbon double bonds (C=C) in its molecule, and " tetraene " refers to have the hydrocarbon compound of four carbon-carbon double bonds (C=C) in its molecule.These carbon-carbon double bonds comprise the carbon-carbon double bond of vinyl carbon-carbon double bond and 5-norbornylene-2-base.

Non-conjugated triolefin or tetraene have three (triolefin situations) or four (tetraene situation) to comprise the carbon-carbon double bond of vinyl and 5-norbornylene-2-base.The hydrogen atom sum that directly is attached to all carbon atoms of close carbon-carbon double bond in non-conjugated triolefin or the tetraene molecule is had no particular limits, still, be preferably 9-33, more preferably 12-33 is preferably 14-33 hydrogen atom.The hydrogen atom sum should obtain having the multipolymer of faster crosslinking reaction speed in this scope.Using two or more different non-conjugated triolefins or tetraene situations, number of hydrogen atoms is the mean number of hydrogen atom.

Among the present invention, be preferably vinyl or 5-norbornylene-2-base key and be incorporated into methylene radical (CH ₂-) non-conjugated triolefin and tetraene.

In these non-conjugated triolefins and the tetraene, better be compound by following general formula (II-a) or general formula (III-a) expression. In this general formula, p and q can be identical or different, and they are 0 or 1 (condition are that p and q can not be 0).

Letter f is the integer of 0-5, better is the integer (condition is that f can not be 0 when p and q are 1) of 0-2.

Letter g is the integer of 1-6, better is the integer of 1-3.

R ¹, R ², R ³, R ⁴, R ⁵, R ⁶And R ⁷Can be identical or different, each naturally hydrogen atom or have 1-5 carbon atom alkyl, better be hydrogen atom or the alkyl that 1-3 carbon atom arranged, better R ¹, R ², R ³, R ⁴, R ⁵And R ⁶Each is hydrogen atom naturally, and R ⁷It is the alkyl of a hydrogen atom or 1-3 carbon atom.、

R ⁸Being hydrogen atom or the alkyl that 1-5 carbon atom arranged, better is the alkyl that 1-3 carbon atom arranged.

R ⁹It is the alkyl of hydrogen atom, a 1-5 carbon atom or by-(CH ₂) _n-CR ¹⁰=CR ¹¹R ¹²(wherein, n is the integer of 1-5, R in expression ¹⁰And R ¹¹Can be identical or different, each is hydrogen atom or the alkyl of 1-5 carbon atom is arranged, R naturally ¹²Be the alkyl of 1-5 carbon atom) group, better be the alkyl of hydrogen atom, a 1-3 carbon atom or by-(CH ₂) _n-CR ¹⁰=CR ¹¹R ¹²(wherein, n is the integer of 1-3, R in expression ¹⁰And R ¹¹Can be identical or different, each is hydrogen atom or the alkyl of 1-3 carbon atom is arranged, R naturally ¹²Be the alkyl of 1-3 carbon atom) group.Yet, when p and q are 1, R ⁹It is the alkyl of a hydrogen atom or 1-5 carbon atom.

Wherein, p, q, f, g and R ¹-R ⁹Have and the identical definition of top general formula (II-a).

Non-conjugated triolefin or tetraene as general formula (II-a) expression specifically have following compound:

6,10-dimethyl-1,5,9-11 carbon triolefins (DMUT)

5,9-dimethyl-1,4,8-12 carbon triolefins (DMDT)

6,9-dimethyl-1,5,8-12 carbon triolefins

6,8,9-trimethylammonium-1,5,8-12 carbon triolefins

6,10,14-trimethylammonium-1,5,9,13-15 carbon tetraenes

6-ethyl-10-methyl isophthalic acid, 5,9-11 carbon triolefins

4-ethylidene-8,12-dimethyl-1,7,11-tridecatriene (EDT)

As non-conjugated triolefin or tetraene by general formula (III-a) expression, specifically have and the non-conjugated triolefin or the described same compound of tetraene of general formula (II-a) expression, vinyl is wherein replaced by 5-norbornylene-2-base.

In the non-conjugated triolefin and tetraene by general formula (II-a) expression, be preferably non-conjugated triolefin or tetraene by general formula (IV-a) expression.These non-conjugated triolefins and tetraene are non-conjugated triolefin and the tetraenes by general formula (II-a) expression, but wherein p is 1, and q is 0.

In the non-conjugated triolefin and tetraene by general formula (III-a) expression, be preferably non-conjugated triolefin or tetraene by general formula (V-a) expression.These non-conjugated triolefins and tetraene are non-conjugated triolefin and the tetraenes by general formula (III-a) expression, but wherein p is 1, and q is 0.

Letter f is the integer of 0-5, better is the integer of 0-2.

Letter g is the integer of 1-6, better is the integer of 1-3.

R ¹, R ², R ⁵, R ⁶And R ⁷Can be identical or different, (II-a) is identical with general formula, better is the alkyl of a hydrogen atom or 1-3 carbon atom, better, R ¹, R ², R ⁵And R ⁶Each is hydrogen atom naturally, and R ⁷It is the alkyl of a hydrogen atom or 1-3 carbon atom.

R ⁸With identical in the general formula (II-a), better be the alkyl of a hydrogen atom or 1-3 carbon atom, be more preferably the alkyl of 1-3 carbon atom.

R ⁹With identical in the general formula (II-a), better be the alkyl of a hydrogen atom or 1-3 carbon atom. Wherein, f, g, R ¹, R ²And R ⁵-R ⁹Have and the identical definition of top general formula (IV-a).Non-conjugated triolefin or tetraene as general formula (IV-a) expression specifically have following compound:

4-ethylidene-1, the 6-octadiene

7-methyl-4-ethylidene-1, the 6-octadiene

7-methyl-4-ethylidene-1, the 6-nonadiene

7-ethyl-4-ethylidene-1, the 6-nonadiene

6,7-dimethyl-4-ethylidene-1,6-octadiene

6,7-dimethyl-4-ethylidene-1,6-nonadiene

4-ethylidene-1, the 6-decadiene

7-methyl-4-ethylidene-1, the 6-decadiene

7-methyl-6-propyl group-4-ethylidene-1, the 6-octadiene

4-ethylidene-1, the 7-nonadiene

8-methyl-4-ethylidene-1,7-nonadiene (EMN)

4-ethylidene-1,7-11 carbon diene

8-methyl-4-ethylidene-1,7-11 carbon diene

7,8-dimethyl-4-ethylidene-1,7-nonadiene

7,8-dimethyl-4-ethylidene-1,7-decadiene

7,8-dimethyl-4-ethylidene-1,7-11 carbon diene

8-methyl-7-ethyl-4-ethylidene-1,6-11 carbon diene

7,8-diethyl-4-ethylidene-1,7-decadiene

9-methyl-4-ethylidene-1, the 8-decadiene

8,9-dimethyl-4-ethylidene-1,8-decadiene

10-methyl-4-ethylidene-1,9-11 carbon diene

9,10-dimethyl-4-ethylidene-1,9-11 carbon diene

11-methyl-4-ethylidene-1,10-12 carbon diene

10,11-dimethyl-4-ethylidene-1,10-12 carbon diene

As non-conjugated triolefin or tetraene by general formula (V-a) expression, specifically have and the non-conjugated triolefin or the described same compound of tetraene of general formula (IV-a) expression, vinyl is wherein replaced by 5-norbornylene-2-base.

Among the present invention, unconjugated polyene (c) is more preferably the compound by general formula (II-a) expression, preferably the compound of being represented by general formula (IV-a).

Above-mentioned non-conjugated triolefin and tetraene can be trans and mixtures cis, also can only be trans or only are the cis forms.

These unconjugated polyenes (c) can use separately, or two or more are used in combination.

By general formula (II-a) and (III-a) the non-conjugated triolefin and the tetraene of expression can adopt known conventional method preparation, for example in the method described in EP0691353A1 and the WO96/20150.

As the alpha-olefin (d) that constitutes a unsaturated olefin base co-polymer 3-20 (iv) carbon atom, specifically have: propylene, 1-butylene, the 1-amylene, the 1-hexene, 3-methyl-1-butene, the 3-Methyl-1-pentene, 3-ethyl-1-amylene, 4-methyl-1-pentene, 4-methyl isophthalic acid-hexene, 4,4-dimethyl-1-hexene, 4,4-dimethyl-1-amylene, 4-ethyl-1-hexene, 3-ethyl-1-hexene, the 1-octene, 1-decene, the 1-dodecylene, tetradecene, cetene, the 1-vaccenic acid, the 1-eicosylene, 9-methyl isophthalic acid-decene, 11-methyl isophthalic acid-dodecylene and 12-ethyl-tetradecene.Wherein, be preferably the alpha-olefin of 4 carbon atoms or more carbon atoms, especially 1-butylene, 1-hexene, 1-octene and 1-decene.These alpha-olefins can use separately, or two or more mix use.

The unsaturated olefin base co-polymer (iv) has structural unit, the structural unit that is derived from aromatic vinyl compound (b) that is derived from ethene (a), the structural unit that is derived from unconjugated polyene (c), and when needing, be derived from the structural unit of the alpha-olefin (d) of 3-20 carbon atom, they are separately with random order combination, this multipolymer has the branched structure that unconjugated polyene (c) causes, and its main chain is line style substantially.Be dissolved in organic solvent and do not contain insoluble part substantially by measuring multipolymer, can determine this multipolymer substantial linear structure and substantially without any gelatinous cross-linked polymer.For example, be dissolved in fully in 135 ℃ of naphthalanes by multipolymer when measuring limiting viscosity [η] and confirm this point.

The unsaturated olefin base co-polymer (iv) in, the structural unit content that is derived from (a) ethene be derived from (d) and the mol ratio ((a)/(d)) of structural unit content of alpha-olefin of 3-20 carbon atom arranged in 100/0 to 60/40 scope, more fortunately 100/0 to 70/30, better in 100/0 to 80/20 scope, and be derived from the structural unit of (a) ethene and be derived from the structural unit total amount and the mol ratio (ethene+alpha-olefin/aromatic vinyl compound) that is derived from the structural unit of aromatic vinyl compound (b) 90/10 to 50/50 scope more fortunately that (d) has the alpha-olefin of 3-20 carbon atom, better 85/15 to 55/45, best 80/20 to 60/40 scope.

Unsaturated olefin base co-polymer iodine number (iv) is preferably 3-50, more preferably 4-40 generally in the 0.5-50 scope.

Calculate according to the fusing point peak value of measuring with difference formula scanning calorimeter, the unsaturated olefin base co-polymer (iv) better has and is less than or equal to 15% degree of crystallinity, better be less than or equal to 10%, the limiting viscosity [η] in 135 ℃ of naphthalane solution is preferably 0.1-10dl/g, more preferably 1-5dl/g.

Be used for unsaturated olefin base co-polymer of the present invention (iv), including two or more structural unit ratios that are derived from the unitary chain structure of continuous structure of aromatic vinyl compound (b) should be smaller or equal to 1%, better smaller or equal to 0.1%.Include two or more unitary chain unit content of continuous structure that are derived from aromatic vinyl compound (b) can by ¹³C-NMR measures.

When the unconjugated polyene (c) of unsaturated olefin base co-polymer in (iv) represented by general formula (II-a), be derived from the unsaturated olefin base co-polymer (iv) in the structural unit of non-conjugated triolefin or tetraene have the structure of following general formula (II-b) expression.

Wherein, p, q, f, g and R ¹-R ⁹Have and the same definition of top general formula (II-a).

During by top general formula (III-a) expression unconjugated polyene (c), be derived from the unsaturated olefin base co-polymer (iv) in the structural unit of non-conjugated triolefin or tetraene have the structure of following general formula (III-b) expression. Wherein, p, q, f, g and R ¹-R ⁹Have and the same definition of top general formula (II-a).

During by general formula (IV-a) expression unconjugated polyene (c), be derived from the unsaturated olefin base co-polymer (iv) in the structural unit of non-conjugated triolefin or tetraene have the structure of following general formula (IV-b) expression. Wherein, f, g, R ¹, R ²And R ⁵-R ⁹Have and the same definition of top general formula (IV-a).

During by general formula (V-a) expression unconjugated polyene (c), be derived from the unsaturated olefin base co-polymer (iv) in the structural unit of non-conjugated triolefin or tetraene have the structure of following general formula (V-b) expression. Wherein, f, g, R ¹, R ²And R ⁵-R ⁹Have and the same definition of top general formula (IV-a).

By measuring multipolymer ¹³C-NMR can determine that the structural unit that is derived from unconjugated polyene (c) has unsaturated olefin base co-polymer recited above arbitrary ad hoc structure (iv).

Unsaturated olefin base co-polymer (iv-a) can be by making being used for copolymerization (a) ethene in the presence of the metallocene catalyst of olefinic polymerization, (b) aromatic vinyl compound, (c) unconjugated polyene and non-essential (d) 3-20 carbon atom.

The method for preparing unsaturated olefin base co-polymer (iv-a) is described in detail in the Japanese Patent Application Publication thing and puts down-10 (1998)-273565.

As the unsaturated olefin base co-polymer modification unsaturated olefin base co-polymer (iv-b) (iv) among the present invention is a kind ofly to go up the soft resin for preparing by unsaturated carboxylic acid or derivatives thereof (below be called unsaturated carboxylic acid etc.) is grafted to unsaturated olefin base co-polymer (iv-a).

Unsaturated carboxylic acid that is used to prepare modified block copolymer (iv-b) etc. is identical with unsaturated carboxylic acid that is used to prepare ethene improved-alpha-olefin-aromatic vinyl compound multipolymer (i-1-b) etc.

With the hydrogenated block copolymer before the graft modification (v-a) is that 100% (weight) is as benchmark, the grafting amount of the unsaturated carboxylic acid in modification unsaturated olefin base co-polymer (iv b) etc. is in 0.01-30% (weight) scope, be preferably 0.01-10% (weight), more preferably 0.1-2% (weight).

Adopt conventional known graft polymerization procedure can finish by the graft modification to unsaturated olefin base co-polymer (iv-a) such as unsaturated carboxylic acid.

The example of ordinary method has: fusion unsaturated olefin base co-polymer (iv-a) also adds unsaturated carboxylic acid etc. therein and carries out the method for graft polymerization reaction and be dissolved in unsaturated olefin base co-polymer (iv-a) in the solvent and add the method that unsaturated carboxylic acid carries out graft polymerization reaction therein.

In these methods, when in the presence of radical initiator, carrying out graft polymerization reaction, the effective grafted monomer of graft polymerization unsaturated carboxylic acid.In this case, be 100 weight parts in unsaturated olefin base co-polymer (iv-a), the radical initiator consumption is generally the 0.001-1 weight part.

Liquid (B)

Be used for liquid of the present invention (B) and be 0.5-100 25 ℃ dynamic viscosity (JIS K-2283), 000cSt, be preferably 100-5,000cSt, 200-1 more preferably, 000cSt, 25 ℃ surface tension (capillary rise test mensuration) is 10-50dyne/cm, be preferably 10-40dyne/cm, more preferably 10-30dyne/cm.As such liquid (B), silicone oil, glycerine, mineral oil, higher alcohols etc. are arranged specifically.As silicone oil, the polysiloxane of repeating unit represented is arranged specifically:

In this formula, R and R ' are alkyl or aryl or the group that hydrogen atom is replaced by halogen atom independently of one another.R and R ' can be identical or different.R and R ' base can part be replaced by hydroxyl or alkoxyl group.

Concrete alkyl has: methyl, ethyl, propyl group, sec.-propyl, normal-butyl, butyl and the tertiary butyl.

Concrete allyl group has phenyl and tolyl.

Concrete halogen atom has: fluorine, chlorine, bromine and iodine.

Concrete alkoxyl group has: methoxyl group, oxyethyl group, propoxy-and isopropoxy.

Good especially in these polysiloxane is polydimethylsiloxane.

Among the present invention, aforesaid liquid (B) can use separately, or two or more are used in combination.

Fine powder (C)

Be used for fine powder of the present invention (C) and be at least a mean particle size smaller or equal to 50 μ m, generally at the 0.1-50 mu m range, be preferably 1-30 μ m, more preferably the organic fine powder of 1-25 μ m or fine silica end.Determine mean particle size with SEM (scanning electronic microscope) or observation by light microscope.

Being used for organic fine powder of the present invention has the fine powder of higher fatty acid or advanced higher fatty acid derivative preferably.

Be used for the saturated or undersaturated higher fatty acid that higher fatty acid of the present invention is preferably 12-30 carbon atom, specifically have: lauric acid, tetradecanoic acid, palmitinic acid, margaric acid, stearic acid, docosoic, oleic acid, linolenic acid, alpha-eleostearic acid, β-eleostearic acid and alpha-linolenic acid.Wherein be preferably stearic acid.

Be used for advanced higher fatty acid derivative of the present invention and be preferably higher fatty acid salt, especially the sodium salt of higher fatty acid, sylvite, magnesium salts, calcium salt, zinc salt, aluminium salt, molysite and lithium salts.Wherein be preferably stearate.As advanced higher fatty acid derivative, also have the acid amides and the ester of higher fatty acid.Wherein, be preferably the acid amides and the ester of stearic acid, erucic acid, oleic acid, methylene-succinic acid and montanic acid.

Above-mentioned higher fatty acid and advanced higher fatty acid derivative can use separately, or two or more are used in combination.

Covering method

In preparing the method that the present invention has good inviscid resin particle, liquid (B) and fine powder (C) cover the particle surface of resin (A).

Covering method is for example:

(1) adopt ordinary method mechanically mixing resin (A) particle and liquid (B), liquid (B) is bonded on the particle, then, (C) is sprinkling upon particle surface with fine powder, so that the method on the surface of liquid (B) and fine powder (C) covering resin (A), or

(2) use is equipped with the tablets press of the what is called " cutting under water " of forcing machine; molten resin in the forcing machine (A) is expressed in the water that contains finely divided liquid (B) and conventional surfactant (as soap) obtains particle; thereby (B) sticks to particle surface with liquid; then; (C) is sprinkling upon particle surface with fine powder, so that the method on the surface of liquid (B) and fine powder (C) covering resin (A).

In the aforesaid method (1), liquid (B) is generally the 50-20 of resin (A) particle weight at the overlay capacity of resin (A) particle surface, and 000ppm is preferably 500-5,000ppm.Fine powder (C) is generally the 50-10 of resin (A) particle weight at the overlay capacity of resin (A) particle surface, and 000ppm is preferably 500-5,000ppm.

In the aforesaid method (2), liquid (B) concentration in water is generally 500-10, and 000ppm weight is preferably 500-5,000ppm weight.The amount of surfactant of using is 100 weight parts in liquid (B) weight, is generally the 1-100 weight part, is preferably the 2-20 weight part.Use the tensio-active agent in this scope can guarantee liquid (B) is dispersed in the water.

In the aforesaid method (2), liquid (B) is generally the 50-20 of resin (A) particle weight at the overlay capacity of resin (A) particle surface, and 000ppm is preferably 500-5,000ppm.Fine powder (C) is generally the 50-10 of resin (A) particle weight at the overlay capacity of resin (A) particle surface, and 000ppm is preferably 500-5,000ppm.

The invention effect

Compare with the resin particle of common olefin-based copolymer rubber etc., the present invention can prepare the resin particle of have good non-sticky (particulate anti-caking effect) and outward appearance and workability.

Embodiment

With way of example explanation the present invention, should be understood that the present invention is not subjected to the restriction of these embodiment below.

Carry out particle caking test in the embodiment of the invention by following method.

[particle caking test]

In the polyethylene bag of 120mm * 210mm, put into 60 gram test particles (every weight in average: about 35 milligrams), with folded 3 times of packing, with the opening of glass paper tape sealed packet.

Then, two bags that fold three times in such a way are stacked in 40 ℃ of environment, place 90g/cm above ²Load, keep after this condition 24 hours, open three folding bags, take out particle, observe the particulate non-sticky, estimate according to following 10 standards.

The inviscid evaluation of＜particle 〉

10: do not lump

7: bonded particulate unclamps under himself weight

5: can bonded particulate be unclamped with hand

3: bonded particulate is unclamped with strong hand-power

1: particle bonds together in bag

Can also the visual inspection particle appearance, and by following zero or * estimate.

＜outward appearance 〉

Zero: do not have powder fine hair (naked eyes can not be distinguished the adding of fine powder (C)).

*: powder fine hair (the energy naked eyes are distinguished the adding of fine powders (C))

Estimate silicone oil and the calcium stearate that is bonded in particle surface among the embodiment according to following mode.

Particularly, after washed with methanol 100 gram particles, the solution of cleaning reclaims fully, uses vaporizer to remove the methyl alcohol component from cleaning solution, by silicon and the calcium in the metal analysis mensuration resistates.Calculate the adhesive capacity of silicone oil and calcium stearate according to metal-salt in the resistates.

Embodiment 1

Mediate ethylene-styrene copolymer (EBRC) [styrene content=36.9% (mole) by using single screw extrusion machine at 200 ℃, ethylene content=63.1% (mole), MFR (ASTM d1238,190 ℃, 2.16 kilogram load)=1 gram is/10 minutes, tensile modulus (YM)=7.0MPa] the 100 weight part particles and the 0.1 weight part silicone oil [trade(brand)name: SH200 that make, TorayDowing Corp. product, dynamic viscosity (20 ℃)=500cSt, surface tension (20 ℃)=20dyne/cm] carry out mechanically mixing by Henschel mixer.

Then, use Henschel mixer, making the surface adhesion that obtains according to top described process that all resins particle of silicone oil and 3,500 weight part mean particle sizes be arranged is the calcium stearate mechanically mixing of 20 μ m.The silicone oil that covers on the thus obtained particle is 980ppm weight.The calcium stearate that covers on the particle that obtains is 3,450ppm weight.

Then, according to the method described above, carry out the particle caking test with this resin particle.

The results are shown in table 1.

Comparative example 1

According to carrying out with embodiment 1 identical step, difference is, do not carry out the mechanically mixing of resin particle and silicone oil and calcium stearate among the embodiment 1.

The results are shown in table 1.

Comparative example 2

According to carrying out with embodiment 1 identical step, difference is, 100 parts by weight resin particles and 0.05 weight part silicone oil mechanically mixing stick to the resin particle surface with silicone oil, but these particles not with the calcium stearate mechanically mixing.

The results are shown in table 1.

Comparative example 3

According to carrying out with embodiment 1 identical step, difference is, do not carry out the mechanically mixing of resin particle and calcium stearate among the embodiment 1.

The results are shown in table 1.

Comparative example 4

According to carrying out with embodiment 1 identical step, difference is, do not carry out the mechanically mixing of resin particle and silicone oil among the embodiment 1.

The results are shown in table 1.

Comparative example 5

According to carrying out with embodiment 1 identical step, difference is, 100 parts by weight resin particles and 0.5 weight part silicone oil mechanically mixing stick to the resin particle surface with silicone oil, but these particles not with the calcium stearate mechanically mixing.

The results are shown in table 1.

Table 1

	Resin	Silicone oil [ppm weight]	Calcium stearate [ppm (weight)]	The caking test result	Outward appearance
	Resin	Silicone oil [ppm weight]	Calcium stearate [ppm (weight)]	The caking test result	Outward appearance	Embodiment 1	????ESRC	????980	????3,450	????5	????○
Comparative example 1	????ESRC	????0	????0	????1	????○	Embodiment 1	????ESRC	????980	????3,450	????5	????○
Comparative example 1	????ESRC	????0	????0	????1	????○	Comparative example 2	????ESRC	????950	????0	????1	????○
Comparative example 3	????ESRC	????960	????0	????1	????○	Comparative example 2	????ESRC	????950	????0	????1	????○
Comparative example 3	????ESRC	????960	????0	????1	????○	Comparative example 4	????ESRC	????0	????3,400	????5	????×
Comparative example 5	????ESRC	????4,600	????0	????1	????○	Comparative example 4	????ESRC	????0	????3,400	????5	????×

Claims

1. has good inviscid resin particle, described particle comprises, (A) at least a be selected from following, (i)-, resin (iv), 23 ℃ of tensile moduluses of these resins, (YM:ATM D-658) is less than or equal to 1600MPa, described particle surface is coated with, (B) at least a 25 ℃ of dynamic viscosities are 0.5-100, the liquid that 000cSt and 25 ℃ of surface tension are 10-50dyne/cm and, (C) be less than or equal to the fine powder of forming by at least a organic fine powder or fine silica end of 50 μ m by mean particle size

(i) the random substantially polymers that closes comprises:

(1) the 1-99% mole is derived from following monomeric polymerized unit;

(a) at least a aromatic vinyl or vinylidene monomer,

(b) at least a aliphatic series of being obstructed or cycloaliphatic vinyl or vinylidene monomer, or

(c) mixture of at least a aromatic vinyl or vinylidene monomer and at least a hindered aliphatic or cycloaliphatic vinyl or vinylidene monomer and

(2) polymerized unit of the alpha-olefin that is derived from an ethene and/or at least a 3-20 of a having carbon atom of 99-1% mole,

(iv) unsaturated olefin base co-polymer, it is to have the alpha-olefin of 3-20 carbon atom to make by copolymerization (a) ethene, (b) aromatic vinyl compound, (c) unconjugated polyene and non-essential (d), wherein, the structural unit content that is derived from (a) ethene be derived from the ratio ((a)/(d)) of structural unit content of alpha-olefin that (d) have 3-20 carbon atom in 100/0 to 60/40 scope, iodine number is in the 0.5-50 scope.

2. one kind prepares the method with good inviscid resin particle as claimed in claim 1, described method comprises: with (B) at least a 25 ℃ of dynamic viscosities is 0.5-100,000cSt and 25 ℃ of surface tension are the liquid of 10-50dyne/cm and the fine powder of being made up of at least a organic fine powder or fine silica end that (C) is less than or equal to 50 μ m by mean particle size, cover (A) at least a particle surface that is selected from the resin of above-mentioned (i)-(iv), 23 ℃ of tensile moduluses (YM:ATM D-658) of these resins are less than or equal to 1600MPa.

3. the method for preparing resin particle as claimed in claim 2 is characterized in that the described polymers (i) that closes is to comprise the random substantially polymers that closes of polymer unit that the 1-99% mole is derived from the alpha-olefin that is derived from least a 3-20 of a having carbon atom of the polymer unit of at least a aromatic vinyl or aromatics vinylidene monomer and 99-1% mole.

4. the method for preparing resin particle as claimed in claim 2 is characterized in that closing polymers (i) and is and comprises the random substantially polymers that closes of polymer unit that the 1-99% mole is derived from the alpha-olefin that is derived from least a 3-10 of a having carbon atom of cinnamic polymer unit and 99-1% mole.

5. the method for preparing resin particle as claimed in claim 2, it is characterized in that closing polymers (i) is to comprise vacation-random polymers that closes that the 1-65% mole is derived from the polymer unit that is derived from ethene of cinnamic polymer unit and 99-35% mole.

6. the method for preparing resin particle as claimed in claim 2, it is characterized in that closing polymers (i) is to comprise the vacation-random polymers that closes that is derived from the ethene and the polymer unit of the alpha-olefin that 3-20 carbon atom arranged that the 1-65% mole is derived from cinnamic polymer unit and 99-35% mole.

7. the method for preparing resin particle as claimed in claim 2 is characterized in that in described resin (A) be 100% weight, and described resin (A) comprises the unsaturated carboxylic acid or derivatives thereof of 0.01-30% weight.

8. the method for preparing resin particle as claimed in claim 2 is characterized in that described liquid (B) is silicoorganic compound.

9. the method for preparing resin particle as claimed in claim 8 is characterized in that described silicoorganic compound are polydimethylsiloxanes.

10. the method for preparing resin particle as claimed in claim 2, it is characterized in that described fine powder (C) be comprise higher fatty acid or advanced higher fatty acid derivative based on organic fine powder.

11. the method for preparing resin particle as claimed in claim 10 is characterized in that described higher fatty acid or advanced higher fatty acid derivative are stearic acid, erucic acid, oleic acid, methylene-succinic acid, montanic acid and their metal-salt, acid amides or ester.