TW461910B - Polymer, process for preparing the same and uses thereof - Google Patents

Abstract

Polymers comprise (A) 5 to 60% by weight of crystalline syndiotactic styrene polymers in the form of nanoparticles, embedded into (B) 40 to 95% by weight of a matrix of atactic styrene polymers, wherein syndiotactic styrene polymers has a syndiotactic fraction, determined by 13C-NMR, greater than 50%.

Description

4 6 19 1 〇 _Case No. 87115505_Year_Month __ V. Description of the invention (1) The present invention relates to a polymer, which contains A) crystalline molecules in the form of nano-particles, which are three-dimensionally aligned ethylene polymers, buried in B) The molecules are irregularly arranged in a styrene polymer matrix. The invention also relates to the preparation of such polymers, their use in the manufacture of fibers, films and castings, and also to the fibers, films and castings obtainable therefrom. Basic styrene has good properties, especially mechanical properties. However, it has insufficient heat resistance at elevated temperatures (approximately 100 ° C), especially in hot water applications. The formulation described in EP-A 3 0 7 4 8 8 includes molecular stereotactic styrene polymers and thermoplastic plastics and / or inorganic fillers. Molecular irregular stereotactic styrene polymers do not exist in the form of nanoparticles but are continuous. phase. Thermoplastic plastics and / or inorganic fillers are used to modify the properties of molecular stereoparallel styrene polymers. The disadvantage is that this gives the engineering material a high melting point and a high thermal distortion temperature (V i c a t). Therefore, the temperature during processing is very high, and it is impossible to use polystyrene for irregular three-dimensional arrangement or toughening of molecules. The formulation disclosed in EP-A 29 1 9 15 consists of molecular stereoparallel styrene polymers (which may contain thermoplastic plastics and / or rubber if required) and specific antioxidants. It is also the same in these formulations, the molecular stereoparallel styrene polymer does not exist in the form of nanoparticles, but a continuous phase, and this results in a high melting point of the mixture and therefore also difficult processing conditions. Therefore, one of the objectives of the present invention is to eliminate the above-mentioned disadvantages and provide a polymer whose heat distortion temperature has not risen, while maintaining good processing properties of a molecularly irregularly arranged styrene polymer. We have found that this goal is achieved with the polymers defined at the beginning.

O: \ 55 \ 55005.ptc Page 4 461910 _ Case No. 87115505 _ month month day__ V. Description of the invention (2) In addition, the method for preparing this type of polymer has been found out, and it is also found out that it is used in the manufacture of fibers and membranes. And castings, and the fibers, membranes, and castings that can be obtained from them. The novel polymer comprises crystalline molecules in the form of nanoparticulates designated as component A). Stereoparallel styrene polymers. For the purposes of the present invention, `` pi crystals '' describes polymers having a degree of crystallinity, measured by a large-angle X-ray diffraction method, of at least 10%, preferably at least 25% and especially at least 50%. The term "η molecular stereo alignment" means that styrene is essentially a molecular stereo alignment, that is, the proportion of molecular stereo alignment is greater than 50%, preferably greater than 60%, as determined by 13C NMR. Component A) is preferably represented by formula I Ethylene aromatic monomer aggregation

Rl — C = CH: 2

Here R1 is hydrogen or υ4-alkyl; R2 to R6 are independent of each other and are C] -C12-alkyl, C6-C18-aryl or halide, or two adjacent radicals occurring together have 4 to 15 A group of carbon atoms. The preferred ones are vinyl aromatic monomers of formula I, where R1 is hydrogen and

O: \ 55 \ 55005.ptc Page 5 4 6 19 1 〇 _Case No. 87115505 Amendment V. Description of the invention (3) R2 to R6 are hydrogen or anthracene, so the styrene is ethylene. The use of an ethylenic aromatic chain, or together, so that the naphthalene derivative form of ethylene, para, m, and p is a different kind of ethylene, which is good for the aromatic monomer monomer composition of the present invention.丨 -C4-Burning group occurs, two adjacent organisms and anthracene-derived preferred compounds-methylstyrene ·-diethyl benzene'ene aromatic aromatic compounds are more aromatic than aromatic compounds. At least two intercalations are obtained, and the resulting monomer can be a formula, a gaseous group, a phenyl group, a biphenyl group, a naphthalene radical, and an example of a compound of formula I having 4 to 12 carbon atoms. Examples are: • Mixtures of p-chlorostyrene, 2, 4, difluorenylbenzene. 4-vinylbiphenyl, vinylnaphthalene and vinyl are also possible, but only preferred. For styrene and p-methylstyrene. The olefin polymer A) includes a star polymer branched by polymerizing the above ethylenically aromatic functional free radicals. I I compounds [Ra-] p ——M-

(II) here

Ra is hydrogen, halogen, or an inert organic radical having up to 20 carbon atoms. Here, if the p ^ 2 radicals may be the same or different, and the two radicals Ra are simultaneously bonded to the metal atom, it may be 3- to 8-membered rings, and if M is a transition metal Ra may be a normal complex ligand,

Rb is hydrogen, (: 丨-(: 4-alkyl or phenyl;

O: \ 55 \ 55005.ptc page 6 461910 _ case number 87115505_ year month day __ 5. Description of the invention (4)

Rc is hydrogen, -alkyl, phenyl, chlorine or an unsaturated hydrocarbon radical having 2 to 6 broken atoms, and M is C, Si, Ge, Sn, B, A1, Ga, N, P, Sb , Ti, Zr, H f, V, Nb 'Ta, Cr, Mo, W, Mn, Fe, Ru, 0s, Co, Rh, I r' Ni, Pd, Pt, Cu, Zn, Cd, n by 2-6,. M is 0-2 0, and p is 0-4, with the proviso: the sum of η + p is equal to the valence of M. For example, these monomers can be prepared from gree (Gr i g n a r d) compounds of chloro (alkyl) styrene and corresponding hydrocarbon compounds, metal compounds, or transition 1 metal compounds (such as halide compounds). Such reactions are described, for example, in K. Nakanishi, J. Chem. Soc. Perkin Trans. I, 199, 3 362, where M is silicon, germanium or tin in this example. Particularly preferred is a block composed of a branched monomer of formula I, where M is carbon, silicon, germanium, tin or titanium, because it is easily available. A preferred index is from 0 to 8, particularly preferably from 0 to 4. It is also possible to use a mixture of different styrene polymers and molecular stereotactic structures of component A), but it is better to use only one vinyl aromatic compound, especially s-PS (molecular stereotactic polystyrene). A styrene polymer having a molecular stereotactic structure and a method for preparing the same are well known to the public and described in, for example, EP-A 5 3 5 5 8 2. In the preparation thereof, a metal dicyclopentadiene is compounded with And co-catalyst. The special metal dicyclopentadiene complexes are pentafluorenyl cyclopentadiene titanium trigas, pentafluorenyl cyclopentadiene trimethyl titanium and pentamethyl cyclopentadiene titanium. Trimethyl ester.

O: \ 55 \ 55005.ptc Page 7 4 6Ί910 _Case No. 87115505_Year Month Day__ V. Description of the invention (5) The styrene polymer with a molecular stereotactic structure usually has a molecular weight Mw (weight average) of 5 0 0 0 to 1 0, 0 0 0, 0 0 0, especially 1 0, 0 0 0 to 2, 0 0 0, 0 0 0. The molecular weight distribution Mw / Mn (average Mn number) is usually in the range of 1.1 to 30, and preferably 1.4 to 10. According to the polymer method, a molecular stereoparallel styrene polymer in the form of nanoparticles can be directly obtained. This is possible, for example by dispersion polymerization, as described in EP-A 643 102. It is better if the dispersion polymerization is carried out using a styrene / stilbene-diene block copolymer as a dispersant, as described in PE-A 44 2 0 9 1 7. Examples of suitable block copolymers with blocks S and B: (SB) n, SBS, BSB, X [(SB) n] m, x [(BS) n] m, X (SBS) m and X ( B-S-B) m, where X is a radical of m-functional coupling agent or m-functional initiator, η is an integer ranging from 1 to 5, and m is an integer ranging from 2 to 20. The diene component suitable for the block B is theoretically an arbitrary diene, but is preferably one having a conjugated double chain. Examples are butadiene, isoprene, difluorenyl butadiene and phenyl butadiene. Diene blocks can be hydrogenated to a certain degree or fully hydrogenated, or unhydrogenated. The molecular weight Mw of the block B is usually in the range from 10,000 to 500,000 g / mole, preferably from 50,000 to 350,000 g / mole and preferably from 7 0,0 0 0 to 2 5 0 , 0 0 0 g / Morteja. Block S consists of an ethylene aromatic monomer copolymer of formula (I) and 1,1-diphenylethylene or a derivative thereof, the derivative having an alkyl group of up to 22 carbon atoms in the aromatic ring if required Substituting from 1 to 4 carbon atoms, such as fluorenyl, ethyl, isopropyl, n-propyl, n-butyl, isobutyl or tert-butyl is preferred. However, the use of unsaturated 1,1-diphenylethylene itself is particularly preferred. In block S

O: \ 55 \ 55005.ptc Page 8 461910 Case No. 87115505 _η Amendment V. Description of the invention (6) It is obtained from 25 to 60% by weight of diphenylethylene, and it is obtained from 1: 1.05 to diphenylethylene. The proportion is preferably in the range of 15 to 65% by weight. Molar ratios of units derived from vinyl aromatic units to units of 1,1_ are usually in the range of 1: 1 to 1:25 1:15, and preferably in the range of 1: 1 to 1.1. 10 Exceptional-The copolymer block s is preferably random and the molecular weight Mw is usually from 20,000 to 50,000, and preferably from 50,000 to 3,000. 〇〇〇 is preferred. The material block S is particularly preferably made of styrene and 1,2-diphenylethylene. The ratio of the blocks S and B is usually in the range of 90:10 to 20:80, and particularly preferably 90i5 to 65:35. After the funeral period, the production capacity can be set t: especially s thief. Therefore, τ 《"degree does not have obvious boundaries, for the purpose of ί phase i PR Β Λ", "transition" transition state is in the transition state, 'adjacent blocks B and S can be freely followed from Shanqi π iL takes people including all other monomers in the age group 0 to M:, Yin can be used to learn from people, use Yin of people: Preparation of people to use, such as description

Press, New York 1983. Fractionation ^ In fact, the Academy alkaloids are preferably starting from phantom organometallic compounds. Compounds, such as methylamine, will be different from lithium. Examples of initiators are lithium alkylated butyllithium and diethyldiphenyllithium, isopropyllithium, n-butyllithium, and the second suitable solvent is p-butylbell or second butyllithium. . Aromatic hydrocarbons are convenient and are inert to the initiators. Examples of the use of aliphatic or aromatic, benzene, and methyl solvents are cyclohexyl, methylcyclohexyl, and diphenylbenzene during dispersion polymerization. Examples of suitable compounds in the 'Polar, Aprotic Substance to Solvent Ether' diisopropyl ether r 1 di are ethers, such as diethylhydrofuran, and tertiary ~ fermented monomethyl bonds, diethylene glycol di Butyl ether or especially four about 0.01 to 5 volume ^ L such as tetramethylethylenediamine or pyridine. Add ’, set well, solvent to non-polar solvent. optimal

461910 ---- Case No. Β71155Π! 年 _ 年月 日 .__. Amendment ________ V. Description of the Invention (7) The amount is 0.1 to 0.3% by volume of tetrahydrofuran. If the molecular stereotactic styrene polymer A) is made into another form, such as a powder, it can be ground by a known method. The final nanoparticle diameter is preferably less than or equal to 2 millimeters, the diameter is preferably in the range of 100 millimeters to 1 millimeter, and most preferably 500 millimeters to 500 micrometers. The novel polymer comprises, as component B), a matrix made of styrene polymers with irregularly arranged molecules. For the purposes of the present invention, " Molecularly irregularly arranged styrene polymers " is unmodified and rubber modified polystyrene, as described in Handbuch der Technischen polymerchemie, 1993, p.475-492 . This type of styrene polymer B), and the method for its preparation, are also described in Kunststoff Handbuch Polystyrol, 4, 1 9 9 6., pp. 109-121 and pp. 2 04-2 1 3, and " Die angewandte makromolekulare Chemie ", 1997, 244, pp. 17-41. Homogeneous polystyrene and toughened polyethylene (HIPS high impact polyethylene) are preferably used as component B). Such products are also commercially available, such as polystyrene 2710, polystyrene 486M, polystyrene 5 85K, Styrolux 6 84D, Styrο 1 ux 6 8 3D, Styrο 1ux 6 5 6C, polystyrene 158K, Polystyrene 16 5H and polystyrene 144C are commercially available from BASF Aktiengesellschaft. In the novel polymer, component A) is preferably 5 to 60% by weight, more preferably 10 to 50% by weight; and component B ) To contain 40 to 95% by weight, and more preferably 50 to 90% by weight. The sum of the weight percentages of component A) and component B) is 100. Novel polymers can be prepared by, for example, physical or chemical mixing methods. For physical mixing methods, the steps are to mix component A) and component B), continuously or batchwise in a reactor at 170 to 260 ° C to 1 7 5 to 2 4 0 ° C, 1 8 0

O: \ 55 \ 55005.ptc Page 10 461910 Correction __mt 87115505 V. Description of the invention (8) to 2 2 0 ° C is best. Examples of suitable reactors are tubular reactors, pressure cookers, kneaders, extruders and vertical reactors, especially extruders. For the chemical mixing method, component A) is dispersed in, for example, styrene (component B) is homogeneous polystyrene), or styrene in which polybutadiene has been dissolved (component B) is Η I P S). The polymerization of styrene can then be carried out by heat or by adding a radical initiator in a known manner and at a temperature of 110 to 26 ° C, preferably 1 15 to 2 40 ° C, and 1 2 0 Optimum to 2 2 0 ° C. It has proven to be better to implement a temperature gradient and use a tandem hybrid container. The resulting polymer can be devolatized in the extruder. If necessary, it is also feasible to add an auxiliary amount of stabilizer (preferably from 0 to 5% by weight of the total novel polymer). Antistatic agents such as those with steric hindrance, antistatic agents such as fatty sulphuric acid or acid succinate, are more suitable for the second group of the periodic table, or nucleating agents, such as benzoate, especially sodium benzoate Or aluminum benzoate. These additives are preferably mixed in an extruder. The novel polymer has a balanced property profile, increased heat distortion temperature, and if component B) is homogeneous polystyrene, it has good fluidity, hardness, and electrical resistance. If component B) is Η I PS, it also has increased heat distortion temperature, low shrinkage, and good toughness and dimensional stability. Novel polymers can be prepared using simple instruments and can be used to make fibers, membranes, and foundries. It is suitable for a wide range of applications, especially in the injection molding and packaging industries. Example component A) s-PS has Mw = 24 0, 200, Mw / Mn = 1.41 and the molecular stereo pair rejection rate is based on 13C NMR> 96%. 3g) In a round bottom flask with an inert atmosphere of nitrogen

O: \ 55 \ 55005.ptc page 11—year M case number 87115505 V. Description of the invention (9) ^ -—-—- Heated to 70 ° C, and with Witrnfi fluorenyl aluminate (MAO) solution . After that, θ / Ear 1 Benzene) after 1 '1 Mor and let (i " h0-5 Mor) pentamethyldi "compound = ^^ plus 9.8 ml of the above MAL0 solution, Titanium-methyl is now δ $ ^ μ @,, t liquid. The internal temperature is adjusted to 70 〇c 1 and continue to order for 1 hour. After that, as reviewed & • It was terminated by adding methyl alcohol. The polymer produced was dried under pressure. The molar mass was determined by high temperature GPC (gel permeation chromatography = analysis method) at 135 C with 1,2,4-trifluorobenzene as solvent. Corrected with a narrow polystyrene standard. The crystallinity of this s-PS was determined to be 52% by wide-angle x-ray diffraction, and was pulverized with a ball mill to a particle size of 800 mm to 2000. Example 1 to 4: Component B is homogeneous polystyrene. Examples 1 and 2: Physical mixing method Example 1 18 kg of homogeneous polystyrene (BASF Aktienges.ellschaft polystyrene 1 5 8 K, according to IS 0 The melt viscosity index measured from 1 1 3 3 is 2.1 to 4.1 1 ml / 10 min (200/5) (90% by weight) in a twin-screw extruder (zsk 25 of Berstorff) at 220 ° C and 2 kg Component A) is mixed (10% by weight) and then made into Shape. I SO standard test piece (150 mm X 10 mm X 4 mm) was injection molded at 220 ° C. Example 2 The procedure of Example 1 was followed, but 14 kg of homogeneous polystyrene (70 weight %) And 6 kg of component A) (30% by weight). Examples 3 and 4: Chemical mixing method Example 3: 2 kg of component A.) (10% by weight) dispersed in 20 kg of 60 t: styrene in,

O: \ 55 \ 55005.ptc Page 12 4 6 19 1 Ο __Case No. 87115505_Year_Month_Revision_. V. Description of the invention (10) Start polymerization with heat, 1 1 0 to 2 2 0 X implementation (By connecting the temperature of three mixing vessels). The brilliants flowed out at 220 ° C in a double-screw extrusion machine (ZSK 25) of Berstorff to remove the volatiles, and then made them spherical. The resulting polymer contained 90% by weight of component B). Example 4: According to the procedure of Example 3, but dissolving 6 kg of component A) (30% by weight) in 16 kg of styrene "to produce a polymer containing 70% by weight of component b) 实例 Examples 5 to 8: Group Sub-B) are HIPS Examples 5 and 6: Physical mixing method Example 5: Follow the steps of Example 1, but use 18 kg Η I PS (B ASF Aktiengesellschaft's polystyrene 48 6M, correct according to DIN 5 3 7 2 6 The viscosity number is 72 to 78 ml / g) (90% by weight) and 2 kg of component A) (10% by weight). Example 6: Following the procedure of Example 5, but using 14 kg of HIPS (70% by weight) and 6 kg of component A) (30 weights). Examples 7 and 8: Chemical mixing method Example 7: Following the steps of Example 3, but dissolving 2 Kg of component A) (10% by weight) in a mixture of 17 · 87 kg of styrene and 1.6 kg of polybutadiene, at the same time of polymerization, the molecules are irregularly arranged in three-dimensional styrene and bonded to polybutadiene on. The resulting polymer contained 90% by weight of component b). Example 8 Following the procedure of Example 7, but dissolving 6 kg of component A) (30% by weight) in

O: \ 55 \ 55005.ptc Page 13 461910 Case No. 87115505_Year_Month____ V. Description of the invention (11) 14.25 kg of styrene and 1.29 kg of polybutadiene. The resulting polymer contained 70% by weight of component B). Comparative Examples 1C to 5C, Comparative Example 1C: Pure s-PS was used and has not been ground into granules. Comparative Example 2C: Pure homogeneous polystyrene (polystyrene 158 K of BASF Aktiengesellschaft) was used. Comparative Example 3C: Using pure HIPS (Polystyrene 48 6M from BASF Aktiengesellschaft) Comparative Example 4C: (in EP 3 0 7 4 88) 2 kg of s-PS (10% by weight) that has not been ground into particles and 18. kg Homogeneous polystyrene (BASF Aktiengesellschaft's polystyrene 158 K) (90% by weight) was mixed as in Example 1 of this application. Comparative Example 5 C: 2 kg of s-PS (10% by weight) which has not been ground into particles, and 18 kg of HIPS (Polypene 486M of BASF Aktiengesellschaft) (90% by weight) are the same as in Example 5. The heat distortion temperatures HDT A and HDT B were measured according to ISO 75.

O: \ 55 \ 55005.ptc page 14 d 6 1 9 1 Ο _ case number 87115505_ year month day _ amendment V. Description of the invention (12)

Example KDT A f ° C] HDT 3 [° C] * 1 83 114 2 89 147 3 39 IIS 4 S9 153 5 83 110 6 33 139 7 88 113 8 89 142 1C 92 245 2C 36 98 3C 79 39 4C 86 100 5C 83 92 O: \ 55 \ 55005.ptc Page 15

Claims (1)

46191 ^ Therefore (# · Year of the Month, Case No. 87115505 Amendments to the Yuan Supplementary Note 6) Application for a patent 1. A polymer comprising A) 5 to 60% by weight of crystalline molecular stereoscopic pairs in the form of nanoparticles Rows of styrenic polymers are buried in B) 40 to 95% by weight of a molecularly irregularly arranged styrenic polymer matrix. 2. The polymer according to item 1 of the scope of patent application, which includes molecularly irregular three-dimensionally arranged homogeneous polystyrene as component B), in which the molecular stereo-alignment ratio of the molecular stereo-aligned styrene polymer is determined by 13C -NMR measurement, greater than 50%. 3. The polymer according to item 1 of the scope of patent application, which includes irregularly arranged molecularly modified rubber modified polystyrene as component B). 4. The polymer according to any one of claims 1 to 3, wherein the particle size of component A) is less than or equal to 2 mm. 5. The polymer according to any one of claims 1 to 3, wherein the crystallinity of component A) is at least 10%. 6. The polymer according to any one of the claims 1 to 3, wherein the content of component A) is 5 to 60% by weight and the content of component B) is 40 to 95% by weight. A method for preparing a polymer according to any one of claims 1 to 3, which comprises mixing 5 to 60% by weight of component A at 170 to 2600 ° C and 40 to 95% by weight of B) ° 8. A method for preparing a polymer according to any one of claims 1 to 3 of the scope of the patent application, wherein 5 to 60% by weight of component A) is dispersed in 40 to 95% by weight of a styrene monomer, and Polymerized at 110 to 260 ° C. 9. A polymer according to any one of claims 1 to 3, which is used for O: \ 55 \ 55005.ptc Page 16 4 6 19 10 O: \ 55 \ 55005.ptc Secret of the 17th page-l〇 repair "ll,. Correction-| Ψ W T9 ** 斯 *;-Cl _ [#; #: 87115505 ^ J —_0〇SLY% Srfx> KL ~ Invention Patent Specification 461910 Chinese polymer, its production method and use, invention name English POLYMER, PROCESS FOR PREPARING THE SAME AND USES THEREOF Name (Chinese) 1. Josef's Note 2. Jog Kreisler 3. Reeve Sharman Inventor's Name (English) 1. JOSEF WUNSCH, 2. JORG KRESSLER 3. RALF TH0MANN Nationality 1. Germany 2. Germany 3. German Residence, Residence 1. 31C, Carton Street, Soested, Germany 2. 16 Ischholz Street, Freiburg, Germany 3. Name 14 (Beijing Lake), Akzie, Germany Name (Chinese) 1. Name (Name) (English) 1. BASF AKTIENGESELLSCHAFT Nationality of the three applicants 1. German residence and residence (office) 1. Schaffen City, Lauenau, Germany [Name of Representative (Chinese) 1. Andres Byberbage 2. Vera. History Tucker Representative Name (English) 1. ANDREAS BIEBERBACH 2. VERA STARK a O: \ 55 \ 55005.ptc Page 1 46191 ^ Therefore (# · Year Month Date Case No. 87115505 Monthly Supplement Amendment Announcement VI. Application for Patent Scope 1. A polymer including A) 5 to 6 0% by weight of crystalline molecules in the form of nano-particulate stereotactic polymers, buried in B) 40 to 95% by weight of the molecularly irregularly arranged styrene polymer matrix. 2. The polymer according to item 1 of the scope of patent application, which includes molecularly irregular three-dimensionally arranged homogeneous polystyrene as component B), in which the molecular stereo-alignment ratio of the molecular stereo-aligned styrene polymer is determined by 13C -NMR measurement, greater than 50%. 3. The polymer according to item 1 of the scope of patent application, which includes irregularly arranged molecularly modified rubber modified polystyrene as component B). 4. The polymer according to any one of claims 1 to 3, wherein the particle size of component A) is less than or equal to 2 mm. 5. The polymer according to any one of claims 1 to 3, wherein the crystallinity of component A) is at least 10%. 6. The polymer according to any one of the claims 1 to 3, wherein the content of component A) is 5 to 60% by weight and the content of component B) is 40 to 95% by weight. A method for preparing a polymer according to any one of claims 1 to 3, which comprises mixing 5 to 60% by weight of component A at 170 to 2600 ° C and 40 to 95% by weight of B) ° 8. A method for preparing a polymer according to any one of claims 1 to 3 of the scope of the patent application, wherein 5 to 60% by weight of component A) is dispersed in 40 to 95% by weight of a styrene monomer, and Polymerized at 110 to 260 ° C. 9. A polymer according to any one of claims 1 to 3, which is used for O: \ 55 \ 55005.ptc Page 16