CN100415796C - Manufacturing process for liquid crystalline polymer - Google Patents
Manufacturing process for liquid crystalline polymer Download PDFInfo
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- CN100415796C CN100415796C CNB2004800250904A CN200480025090A CN100415796C CN 100415796 C CN100415796 C CN 100415796C CN B2004800250904 A CNB2004800250904 A CN B2004800250904A CN 200480025090 A CN200480025090 A CN 200480025090A CN 100415796 C CN100415796 C CN 100415796C
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- acid
- dicarboxylic acid
- liquid crystalline
- crystalline polymers
- lcp
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Links
- 229920000106 Liquid crystal polymer Polymers 0.000 title claims abstract description 74
- 238000004519 manufacturing process Methods 0.000 title description 5
- OFOBLEOULBTSOW-UHFFFAOYSA-N Malonic acid Chemical compound OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 claims abstract description 51
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 46
- 238000000034 method Methods 0.000 claims description 31
- -1 aliphatic diester Chemical class 0.000 claims description 26
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 26
- KKEYFWRCBNTPAC-UHFFFAOYSA-N Terephthalic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-N 0.000 claims description 22
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 claims description 21
- 150000001875 compounds Chemical class 0.000 claims description 14
- FJKROLUGYXJWQN-UHFFFAOYSA-N 4-hydroxybenzoic acid Chemical compound OC(=O)C1=CC=C(O)C=C1 FJKROLUGYXJWQN-UHFFFAOYSA-N 0.000 claims description 12
- BVKZGUZCCUSVTD-UHFFFAOYSA-N carbonic acid Chemical class OC(O)=O BVKZGUZCCUSVTD-UHFFFAOYSA-N 0.000 claims description 12
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 claims description 9
- 125000003118 aryl group Chemical group 0.000 claims description 9
- 229940090248 4-hydroxybenzoic acid Drugs 0.000 claims description 6
- IISBACLAFKSPIT-UHFFFAOYSA-N bisphenol A Chemical compound C=1C=C(O)C=CC=1C(C)(C)C1=CC=C(O)C=C1 IISBACLAFKSPIT-UHFFFAOYSA-N 0.000 claims description 6
- QQVIHTHCMHWDBS-UHFFFAOYSA-N isophthalic acid Chemical compound OC(=O)C1=CC=CC(C(O)=O)=C1 QQVIHTHCMHWDBS-UHFFFAOYSA-N 0.000 claims description 6
- RXOHFPCZGPKIRD-UHFFFAOYSA-N naphthalene-2,6-dicarboxylic acid Chemical compound C1=C(C(O)=O)C=CC2=CC(C(=O)O)=CC=C21 RXOHFPCZGPKIRD-UHFFFAOYSA-N 0.000 claims description 6
- GHMLBKRAJCXXBS-UHFFFAOYSA-N resorcinol Chemical compound OC1=CC=CC(O)=C1 GHMLBKRAJCXXBS-UHFFFAOYSA-N 0.000 claims description 6
- 239000000126 substance Substances 0.000 claims description 6
- 239000002253 acid Substances 0.000 claims description 5
- 230000015572 biosynthetic process Effects 0.000 claims description 5
- UOBYKYZJUGYBDK-UHFFFAOYSA-N 2-naphthoic acid Chemical compound C1=CC=CC2=CC(C(=O)O)=CC=C21 UOBYKYZJUGYBDK-UHFFFAOYSA-N 0.000 claims description 4
- KAUQJMHLAFIZDU-UHFFFAOYSA-N 6-Hydroxy-2-naphthoic acid Chemical compound C1=C(O)C=CC2=CC(C(=O)O)=CC=C21 KAUQJMHLAFIZDU-UHFFFAOYSA-N 0.000 claims description 4
- 238000006243 chemical reaction Methods 0.000 claims description 4
- NEQFBGHQPUXOFH-UHFFFAOYSA-N 4-(4-carboxyphenyl)benzoic acid Chemical compound C1=CC(C(=O)O)=CC=C1C1=CC=C(C(O)=O)C=C1 NEQFBGHQPUXOFH-UHFFFAOYSA-N 0.000 claims description 3
- 229940106691 bisphenol a Drugs 0.000 claims description 3
- 235000019439 ethyl acetate Nutrition 0.000 claims description 3
- LCQXXVFFJHBYME-UHFFFAOYSA-N 2-butyl-4-hydroxybenzoic acid Chemical group CCCCC1=CC(O)=CC=C1C(O)=O LCQXXVFFJHBYME-UHFFFAOYSA-N 0.000 claims description 2
- UFMBOFGKHIXOTA-UHFFFAOYSA-N 2-methylterephthalic acid Chemical compound CC1=CC(C(O)=O)=CC=C1C(O)=O UFMBOFGKHIXOTA-UHFFFAOYSA-N 0.000 claims description 2
- GWZCCUDJHOGOSO-UHFFFAOYSA-N diphenic acid Chemical compound OC(=O)C1=CC=CC=C1C1=CC=CC=C1C(O)=O GWZCCUDJHOGOSO-UHFFFAOYSA-N 0.000 claims 1
- HRRDCWDFRIJIQZ-UHFFFAOYSA-N naphthalene-1,8-dicarboxylic acid Chemical compound C1=CC(C(O)=O)=C2C(C(=O)O)=CC=CC2=C1 HRRDCWDFRIJIQZ-UHFFFAOYSA-N 0.000 claims 1
- 150000002009 diols Chemical class 0.000 abstract description 5
- 150000002148 esters Chemical class 0.000 abstract description 5
- 238000000465 moulding Methods 0.000 abstract description 3
- 239000011347 resin Substances 0.000 abstract description 3
- 229920005989 resin Polymers 0.000 abstract description 3
- 239000000203 mixture Substances 0.000 description 23
- 238000006116 polymerization reaction Methods 0.000 description 9
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 8
- 229910052799 carbon Inorganic materials 0.000 description 6
- 230000000052 comparative effect Effects 0.000 description 6
- 238000005516 engineering process Methods 0.000 description 6
- 229920000728 polyester Polymers 0.000 description 6
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 5
- 239000000155 melt Substances 0.000 description 5
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 4
- 238000002156 mixing Methods 0.000 description 4
- 239000007787 solid Substances 0.000 description 4
- 150000001721 carbon Chemical group 0.000 description 3
- 125000000524 functional group Chemical group 0.000 description 3
- 150000002894 organic compounds Chemical class 0.000 description 3
- WFDIJRYMOXRFFG-UHFFFAOYSA-N Acetic anhydride Chemical compound CC(=O)OC(C)=O WFDIJRYMOXRFFG-UHFFFAOYSA-N 0.000 description 2
- 101000596046 Homo sapiens Plastin-2 Proteins 0.000 description 2
- 101000762938 Homo sapiens TOX high mobility group box family member 4 Proteins 0.000 description 2
- 239000004698 Polyethylene Substances 0.000 description 2
- 102100026749 TOX high mobility group box family member 4 Human genes 0.000 description 2
- 229910010413 TiO 2 Inorganic materials 0.000 description 2
- 150000007933 aliphatic carboxylic acids Chemical class 0.000 description 2
- 125000001931 aliphatic group Chemical group 0.000 description 2
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 2
- 150000005690 diesters Chemical class 0.000 description 2
- 238000004821 distillation Methods 0.000 description 2
- 125000004185 ester group Chemical group 0.000 description 2
- 238000001125 extrusion Methods 0.000 description 2
- 230000004927 fusion Effects 0.000 description 2
- 239000003365 glass fiber Substances 0.000 description 2
- 238000005469 granulation Methods 0.000 description 2
- 230000003179 granulation Effects 0.000 description 2
- 238000001746 injection moulding Methods 0.000 description 2
- 239000004973 liquid crystal related substance Substances 0.000 description 2
- 239000000314 lubricant Substances 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 239000000178 monomer Substances 0.000 description 2
- 229920000573 polyethylene Polymers 0.000 description 2
- 238000002360 preparation method Methods 0.000 description 2
- 238000010008 shearing Methods 0.000 description 2
- 239000004408 titanium dioxide Substances 0.000 description 2
- 150000004684 trihydrates Chemical class 0.000 description 2
- LNETULKMXZVUST-UHFFFAOYSA-N 1-naphthoic acid Chemical compound C1=CC=C2C(C(=O)O)=CC=CC2=C1 LNETULKMXZVUST-UHFFFAOYSA-N 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 229920000049 Carbon (fiber) Polymers 0.000 description 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- 101001090688 Homo sapiens Lymphocyte cytosolic protein 2 Proteins 0.000 description 1
- 102100034709 Lymphocyte cytosolic protein 2 Human genes 0.000 description 1
- 125000000217 alkyl group Chemical group 0.000 description 1
- 229920006231 aramid fiber Polymers 0.000 description 1
- PWHCIQQGOQTFAE-UHFFFAOYSA-L barium chloride dihydrate Chemical compound O.O.[Cl-].[Cl-].[Ba+2] PWHCIQQGOQTFAE-UHFFFAOYSA-L 0.000 description 1
- 238000007664 blowing Methods 0.000 description 1
- PASHVRUKOFIRIK-UHFFFAOYSA-L calcium sulfate dihydrate Chemical compound O.O.[Ca+2].[O-]S([O-])(=O)=O PASHVRUKOFIRIK-UHFFFAOYSA-L 0.000 description 1
- 239000006229 carbon black Substances 0.000 description 1
- 239000004917 carbon fiber Substances 0.000 description 1
- 150000001733 carboxylic acid esters Chemical class 0.000 description 1
- 238000013329 compounding Methods 0.000 description 1
- 238000000748 compression moulding Methods 0.000 description 1
- 238000009833 condensation Methods 0.000 description 1
- 230000005494 condensation Effects 0.000 description 1
- 238000006482 condensation reaction Methods 0.000 description 1
- JZCCFEFSEZPSOG-UHFFFAOYSA-L copper(II) sulfate pentahydrate Chemical compound O.O.O.O.O.[Cu+2].[O-]S([O-])(=O)=O JZCCFEFSEZPSOG-UHFFFAOYSA-L 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 230000008020 evaporation Effects 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- JEIPFZHSYJVQDO-UHFFFAOYSA-N ferric oxide Chemical compound O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 description 1
- 239000000835 fiber Substances 0.000 description 1
- 239000000945 filler Substances 0.000 description 1
- 238000011049 filling Methods 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 239000005337 ground glass Substances 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 238000004898 kneading Methods 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 1
- 239000010445 mica Substances 0.000 description 1
- 229910052618 mica group Inorganic materials 0.000 description 1
- 238000005457 optimization Methods 0.000 description 1
- 229920006280 packaging film Polymers 0.000 description 1
- 239000012785 packaging film Substances 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 239000000049 pigment Substances 0.000 description 1
- 238000006068 polycondensation reaction Methods 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 238000004080 punching Methods 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000001175 rotational moulding Methods 0.000 description 1
- 125000000467 secondary amino group Chemical class [H]N([*:1])[*:2] 0.000 description 1
- 125000000547 substituted alkyl group Chemical group 0.000 description 1
- 229910052623 talc Inorganic materials 0.000 description 1
- 239000000454 talc Substances 0.000 description 1
- 235000012222 talc Nutrition 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 1
- 239000012745 toughening agent Substances 0.000 description 1
- 239000003643 water by type Substances 0.000 description 1
Landscapes
- Polyesters Or Polycarbonates (AREA)
Abstract
The properties of a liquid crystalline polymer (LCP) containing ester linkages and made in the presence of an excess of diol are improved by treating the LCP with a dicarboxylic acid at elevated temperature. The resulting LCPs are useful as molding resins and for films.
Description
Technical field
The present invention relates to the method for production liquid crystalline polymers.This method provides has the liquid crystalline polymers of improving performance.This method comprises aliphatic ester and the randomly hydroxycarboxylic acid reaction that makes dicarboxylic acid and glycol, wherein has excessive glycol (ester), and handles the LCP that obtains with dicarboxylic acid.
Background technology
Liquid crystalline polymers (LCP) is the annual commodity of making thousands of tons of.They are used for many aspects, as moulding resin with in film, for example make Electrical and Electronic part, auto parts and medical part.LCP is the most normal to be provided with the polyester form, but also can obtain with poly-(ester-acid amide) form.Form the condensation reaction of polyester key the most common by at high temperature making one or more dicarboxylic acid and one or more glycol aliphatic ester and/or the aliphatic mono condensation of one or more hydroxycarboxylic acids finish.Though this aliphatic ester can " be pre-formed ", that is to say, adds batching to polymerization technique with the aliphatic ester form, because economic cause, the common original position manufacturing of aliphatic ester forms aliphatic ester by an amount of aliphatic carboxylic acid acid anhydride is added in the polyblend.
Usually, form the required whole monomers of LCP and be added into reactor, have the ester group and the hydroxycarboxylic acid monomer that is present in this ester group of whole glycol hydroxyl with formation with a certain amount of aliphatic carboxylic acid acid anhydride (being generally diacetyl oxide).Heated mixt is removed formed carboxylic acid with the formation of finishing ester and by distillation.Follow the distillation of carboxylic acid, continue heating and carry out polycondensation and finally apply vacuum usually to finish polymerization.Perhaps, can interrupt melt polymerization and use so-called solid state polymerization will be somebody's turn to do the molecular weight that (in advance) polymers is aggregated to expectation further at certain point.It is slightly volatile working as one of used glycol especially, perhaps wishes to use in polymerization excessive glycol to compensate owing to any possible loss of glycol (perhaps its diester) that is brought of removing in casual volatilization and the polymerization.Yet the LCP that is obtained may not have and requiredly uses best performance, and to compare with some desired application especially may be more frangible.
United States Patent (USP) 6,294,618 have described with multiple functional compound processing LCP to reduce the viscosity of LCP.
Have and improve performance as stretching or the LCP of flexural elongation is desirable.
Summary of the invention
The present invention relates to make the method for liquid crystalline polymers (LCP).Do not mention with the excess diol that exists and make LCP, do not have yet
One aspect of the present invention is that a kind of method comprises:
(a) form liquid crystalline polymers by batching, described batching comprises the aliphatic diester of one or more first dicarboxylic acid, one or more first glycol and the aliphatic ester of one or more hydroxycarboxylic acids randomly; With
(b) make liquid crystalline polymers and every kilogram of about 2～about 200 millinormal second dicarboxylic acid of described liquid crystalline polymers contact for some time being enough to cause under the temperature of second dicarboxylic acid and liquid crystalline polymers reaction, it is enough to make the tensile elongation increase about at least 10% of liquid crystalline polymers;
Condition is that the mol ratio of the total amount of the total amount of existing first glycol and first dicarboxylic acid is 1.01 or bigger.
Embodiment
Used some terms in this article, they are described below.
So-called liquid crystalline polymers is meant and shows anisotropic polymkeric substance in TOT or any similar test method (as United States Patent (USP) 4,075, described in 262, therefore it be incorporated herein by reference).Preferred polymkeric substance is a liquid crystal polyester, and further preferably liquid crystal polyester is an aromatic polyester.Aromatic polyester is meant at the carbon of ester bond-C (O) O-group end and Sauerstoffatom and is bonded to aromatic ring carbon atom partly separately.
Glycol is meant the organic compound with two hydroxyls, and it does not preferably have the functional group that other can form ester bond.Preferred diol is an aromatic diol, and wherein two hydroxyl bonds are incorporated into the carbon atom of one or two different kinds of aromatic ring.
Dicarboxylic acid is meant the organic compound with two carboxyls, and it does not preferably have the functional group that other can form ester bond.The optimization acid is an aromatic dicarboxylic acid, and wherein two carboxyls are bonded to the carbon atom of one or two different kinds of aromatic ring.
Hydroxycarboxylic acid is meant the organic compound with a hydroxyl and a carboxyl, and it does not preferably have the functional group that other can form ester bond.Preferred hydroxycarboxylic acid is an aromatic hydroxy-carboxylic, and wherein hydroxyl and carboxyl are bonded to the carbon atom of one or two different kinds of aromatic ring.
The aliphatic diester of glycol is meant by two pure and mild two carboxyl (R derived from aliphatic carboxylic acid
1CO
2-, R wherein
1Be alkyl or substituted alkyl) diester that forms.The aliphatic ester of hydroxycarboxylic acid is meant the monoesters that is formed derived from the carboxyl of aliphatic carboxylic acid by hydroxycarboxylic acid and.Preferred partly or entirely above-mentioned ester is an acetic ester.
" tensile elongation " is meant and works as by the measured extension at break of ASTM Method D638 that it uses the extension speed and the I type bar of 5.1 millimeters/minute (0.2 inch per minutes).Use strain gage to measure accurately to measure little breaking strain usually.
Handle the useful dicarboxylic acid of LCP and comprise terephthalic acid, 2,6-naphthalic acid, m-phthalic acid, 4,4 '-diphenic acid, 2-methyl terephthalic acid and hexanodioic acid.Preferred dicarboxylic acid is a m-phthalic acid, 2,6-naphthalic acid and terephthalic acid, and terephthalic acid and 2, and the 6-naphthalic acid is particularly preferred.Other preferred second dicarboxylic acid is an aromatic dicarboxylic acid, and wherein two carboxyls are bonded directly to aromatic ring carbon atom.
Comprise terephthalic acid, m-phthalic acid, 2 as the monomeric useful dicarboxylic acid of LCP, 6-naphthalic acid, 4,4 '-diphenic acid and 1, the 8-naphthalic acid.As the monomeric useful glycol of LCP comprise ethylene glycol, quinhydrones, Resorcinol, 4,4 '-xenol, 2,6-dihydroxy naphthlene, 1,8-dihydroxy naphthlene, bisphenol-A and bis-phenol-S.Quinhydrones and 4,4 '-xenol is that preferred glycol and quinhydrones are particularly preferred.Comprise 4-hydroxy-benzoic acid, 6-hydroxyl-2-naphthoic acid (napthoic acid) and tertiary butyl-4-hydroxy phenylformic acid as the monomeric useful hydroxycarboxylic acid of LCP.Preferred hydroxycarboxylic acid is 4-hydroxy-benzoic acid and 6-hydroxyl-2-naphthoic acid, and the 4-hydroxy-benzoic acid is particularly preferred.
When making LCP, the mol ratio of total diol and total dicarboxylic acid is 1.01 or bigger (the excessive at least 1mol% of existing glycol), preferred 1.02 or bigger and preferred especially 1.03 or bigger.Preferably, total diol is about 1.5 or littler with the mol ratio of total dicarboxylic acid, more preferably about 1.10 or littler.Any lower limit of glycol and any upper limit can be combined and form preferable range.
In the preferred method of preparation LCP, LCP prepares under fusion fully, handles with dicarboxylic acid then.In another preferred method, LCP prepares under fusion at first, improves the molecular weight of LCP then in solid state polymerization.Handle LCP with dicarboxylic acid behind the solid state polymerization.
When LCP was in molten state, it was the most effective handling LCP with dicarboxylic acid.In a preferred method, LCP is fused and mixes with dicarboxylic acid at the melt mixer that is used for polymkeric substance such as list or twin-screw extruder or kneading machine.Heated mixt is to more than the LCP melting temperature, in the amount increase of elongation to expect of this temperature LCP when mixture is heated and mix in mixing tank.Though do not desire to make the present invention to be subjected to the restriction of any theory especially or mechanism, believe when dicarboxylic acid arrive certain temperature (in this temperature, its can with other substance reactions that are present in the melt) time, the elongation of LCP increases.LCP and dicarboxylic acid can be before being passed into mixing tank with solid-state form by pre-mixing, perhaps can be added respectively and in mixing tank, mix.
Other materials for example filler, toughener, lubricant, pigment and other material that becomes known for making LCP can be sneaked into LCP simultaneously with dicarboxylic acid.In experimental measurement, the elongation of LCP (comprise other sneak into the batching of LCP) with have same composition and with the same manner manufacturing but there is not the elongation of the LCP of dicarboxyl to compare.Perhaps, can at first prepare the composition that comprises LCP and other batchings, handle with dicarboxylic acid then.The elongation of the LCP that obtains is compared with the elongation of handling with the same manner but not adding the same combination of dicarboxylic acid." pure " LCP can with dicarboxylic acid handle and its elongation with the same manner but do not use the elongation of dicarboxyl acid-treated " pure " LCP to compare.
The example of other useful batchings comprises for example polyethylene wax of glass fibre, ground glass fibre, hollow or solid glass spheroid, mica, talcum, titanium dioxide, carbon black, carbon fiber and aramid fiber and lubricant.
The amount of used (second) dicarboxylic acid is for about at least 2, preferably about at least 5 (milliequivalent)/kg LCP (only based on LCP).The amount of (second) dicarboxylic acid that is added in LCP handles is about 200 or still less, preferably approximately 100 or still less, and more preferably about 50 or (milliequivalent)/kg LCP (the only LCP in composition) still less." equivalent " is meant the equivalent of carboxylic functionality, and the dicarboxylic acid of a mmole comprises two millinormal carboxyls.Any lower limit of dicarboxylic acid content and any upper limit can be combined and form preferable range.
The difunctional compound of other types can be used to add to the dicarboxylic acid that is used for handling LCP.Functionality in above-claimed cpd can comprise hydroxyl, carboxylicesters, ester and uncle or secondary amine, and hydroxyl is preferred.Useful oxy-compound comprises two alcohol and waters (according to the difunctional compound that defines) herein, and aromatic diol is particularly preferred in the glycol.Useful aromatic diol comprise quinhydrones, Resorcinol, 4,4 '-xenol, 2,6-dihydroxy naphthlene, 1,8-dihydroxy naphthlene, bisphenol-A and bis-phenol-S.Above-mentioned preferred aromatic diol be quinhydrones and 4,4 '-xenol, 4,4 '-xenol is particularly preferred.
Water also is particularly preferred oxy-compound, and can be used in combination separately or with glycol, particularly aromatic diol.With water or with the form of the water that produces under processing condition, water can be added in the technology.For example, water can with hydrate or under technology (temperature) condition the form of other compounds of " mistake " water be added into.Above-mentioned hydrate and other compounds comprise hibbsite, Salzburg vitriol, barium chloride dihydrate and calcium sulphate dihydrate.
(do not comprise water, if present) integral molar quantity is no more than the twice of the integral molar quantity of handling the dicarboxylic acid that LCP added, the more preferably about 100mol% of about 20-of the amount of about above-mentioned dicarboxylic acid that adds to preferred other difunctional compounds.If there is water, it can be compared many a lot of amounts with the integral molar quantity of second dicarboxylic acid that is added and be added, and it is independent of and does not comprise the difunctional compound that any other added.If make water, it is 0.2 with the mol ratio with the dicarboxylic acid that is added preferably: 1-used in about 10: 1.That is to say that the water yield is preferably the about 1000mol% of about 20-based on the mole number of second dicarboxylic acid.The water yield in the hydrate is only got and is done that " emancipated " is d/d amount under the technology condition.For example, under the certain temperature condition, trihydrate only every mole of trihydrate produces two mole of water.May need the bigger water yield because be not the water that all added be effective in technology.If be added rather than original position produces as water, many (if not most of) water may be lost, because its potential evaporation and/or be not fairly soluble in the technology batching.To being contained in the water in the hydrate, equally so (possible degree is less).Under given set technique condition, amount can be by simple measuring for the water that required realization certain viscosity reduces (perhaps hydrate, because water may exist with the form of combination water).Have been noted that water (needing hydrate) amount is to a certain extent by the scale of equipment used and/or " stopping property " of this equipment (tendency of loss water vapour) mensuration.
When existing with moderate, amount as noted before, other difunctional compound (particularly oxy-compound) be considered to reduce LCP melt viscosity and to other physicals disadvantageous effect greatly not of LCP.Some melts form operational example such as injection-molded in, be favourable than low melt viscosity, because it can provide easier and/or more complete mold filling, if particularly model has narrow or thin opening or path.
When LCP handled with dicarboxylic acid, it is about at least 10% that the LCP tensile elongation preferably increases, and more preferably about at least 20%.Use following formula to calculate the per-cent that elongation increases:
Wherein, EAT is the per-cent tensile elongation after (using dicarboxylic acid) handles, and EBT is the per-cent tensile elongation before handling.
LCP can be used as the moulding resin, for example, is used to make formation of parts, and it is used for electric/electronic device, Motor vehicles, medical device and packaging film.Making formation of parts can be by making the composition melt forming that contains LCP, for example injection-molded by injection-molded, extruding, blowing, punching press, rotational molding and compression molding.Film can make by straight die or by the rotating mold extruding.
Embodiment
In the following embodiments, (KaynessCorp., Morgantown PA USA.), are 1000/ second mensuration melt viscosity down in 350 ℃ (unless otherwise mentioned) and shearing rate to use Kayness Model 8052 viscometers.By ASTM D638 method, use I shape specimen shape, thick (1/8 ") and extension speed are to measure tensile property under the condition of 0.51 centimeters/minute (0.2 inch per minute) for 0.32cm at sample.Use strain gage to test accurately to measure little breaking strain usually.
In an embodiment, except that indicating, all umber is a weight part.
In an embodiment, use following raw materials according:
The ATH-hibbsite
BP-4,4 '-xenol
GF-
991 glass fibre can be available from Saint-Gobain VetrotexAmerica, Valley Forge, and PA 19482, USA.
The LCP1-liquid crystalline polymers, preparation is from quinhydrones/terephthalic acid/2,6-naphthalic acid/4-hydroxy-benzoic acid 100/30/70/150 molar part, wherein the initial ratio of quinhydrones and dicarboxylic acid is 1.05, and diacetyl oxide added in the polymerization process forms aliphatic acetic ester with original position.
The liquid crystalline polymers of LCP2-such as LCP1, different is is polymerized to more compounding after the high molecular.
Lube-
V PE190 polyethylene wax can be available from Clarient Corp., Charlotte, and NC 28205, USA.
NDA-2, the 6-naphthalic acid.
The MV-melt viscosity, the Pas of unit, 1000 seconds
-1Shearing rate.
The elongation of Ten.Elong.-tension fracture, %.
The Ten.Mod-tensile modulus, GPa.
The Ten.Str.-tensile strength, MPa.
TiO
2-
R-100 titanium dioxide can derive from E.I.DuPont de Nemours﹠amp; Co., Inc., Wilmington, DE 19898, USA.
The TPA-terephthalic acid.
Embodiment 1-11 and comparative example A-E
All composition comprises 2.0%TiO
2(embodiment 11 comprises 4.0%TiO
2), 0.2%Lube, 45.0%GF, the amount of BP and TPA (based on the weight percentage of total composition) is shown in Table 1, all the other are LCP1.Said composition is mixed on 30mmWerner and Pfleiderer twin-screw extruder with the 275rpm helix speed.For embodiment 1-7 and comparative example A and B, the sleeve temperature is 360,370,370,320,300,300,320,330 ℃ (sleeve 2-8 and moulds), and for embodiment 8-11 and Comparative Examples C-E, sleeve 2-8 is 310 ℃ (330 ℃ on moulds).When extrusion machine withdraws from, composition is by granulation.Spherolite is formed as testpieces on the Arberg of 1.5oz injection moulding machine.For embodiment 1-7 and comparative example A and B, the sleeve temperature is 330 ℃, and for embodiment 8-11 and Comparative Examples C-E, the sleeve temperature is 320 ℃.The mould temperature all is 70 ℃.Press tensile property and measure the melt viscosity of composition, the results are shown in Table 1.
Table 1
| Embodiment | TPA | BP | MV | Ten. Mod. | Ten. Str. | Ten. Elong. |
| A | 0.0 | 0.0 | 36 | 15.3 | 116 | 2.4 |
| B | 0.0 | 0.2 | 22 | 13.5 | 113 | 2.4 |
| 1 | 0.4 | 0.0 | 28 | 11.0 | 108 | 3.7 |
| 2 | 0.6 | 0.0 | 19 | 11.4 | 107 | 3.7 |
| 3 | 0.5 | 0.1 | 21 | 12.0 | 107 | 3.5 |
| 4 | 0.4 | 0.2 | 22 | 12.7 | 107 | 3.5 |
| 5 | 0.1 | 0.1 | 20 | 12.6 | 123 | 3.4 |
| 6 | 0.2 | 0.2 | 20 | 13.1 | 112 | 3.5 |
| 7 | 0.3 | 0.3 | 17 | 12.5 | 110 | 3.4 |
| C | 0.0. | 0.0 | 41 | 13.0 | 114 | 3.1 |
| D | 0.0. | 0.3 | 20 | 12.0 | 106 | 3.0 |
| E | 0.0 | 0.6 | 11 | 13.0 | 102 | 2.6 |
| 8 | 0.8 | 0.0 | 19 | 10.3 | 113 | 3.9 |
| 9 | 0.4 | 0.2 | 25 | 11.2 | 115 | 3.6 |
| 10 | 0.4 | 0.4 | 14 | 10.8 | 118 | 4.0 |
| 11 | 0.4 | 0.4 | 15 | 12.0 | 115 | 4.1 |
Flexural property test demonstrate to tension test in the similar trend of result that obtains.Although have than corresponding wherein TPA and the lower melt viscosity of all non-existent composition of BP, compare with the composition that does not contain TPA or only contain BP, contain TPA composition (no matter whether BP exists) and have higher tension fracture elongation.This shows that the composition that contains TPA is than other composition flexible more.In addition, the composition color slightly shallow (whiter) that contains TPA and BP.
Embodiment 12-19 and Comparative Examples F
All composition comprises 2.0%TiO2,0.2%Lube, 45.0%GF, and the amount of NDA, BP and ATH (in the weight percentage of total composition) is shown in Table 2, and all the other are LCP2.Said composition is mixed on 30mm Werner and Pfleiderer twin-screw extruder with the 225rpm helix speed.The sleeve temperature is 360,360,360,360,360,330,330,330,330 ℃ (sleeve 2-9 and die heads).When extrusion machine withdraws from, composition is by granulation.Spherolite is formed as testpieces on the Arberg of 1.5oz injection moulding machine.The sleeve temperature is 330 ℃ and the mould temperature all is 70 ℃.By the melt viscosity (measuring in 340 ℃) of tensile property mensuration composition, the results are shown in Table 2.
Table 2
| Embodiment | NDA | BP | ATH | MV | Ten Mod | Ten Str | Ten Elong |
| F | 0.00 | 0.00 | 0.00 | 54 | 15.3 | 125 | 3.2 |
| 12 | 0.06 | 0.00 | 0.00 | 58 | 16.2 | 136 | 4.1 |
| 13 | 0.06 | 0.06 | 0.00 | 47 | 15.0 | 133 | 3.8 |
| 14 | 0.06 | 0.18 | 0.00 | 45 | 15.3 | 110 | 2.7 |
| 15 | 0.06 | 0.00 | 0.02 | 52 | 16.8 | 131 | 3.7 |
| 16 | 0.06 | 0.00 | 0.06 | 40 | 16.5 | 136 | 4.0 |
| 17 | 0.06 | 0.00 | 0.08 | 41 | 16.1 | 134 | 3.9 |
| 18 | 0.06 | 0.06 | 0.03 | 38 | 16.7 | 132 | 3.5 |
| 19 | 0.06 | 0.06 | 0.06 | 37 | 16.5 | 136 | 3.8 |
Claims (20)
1. method comprises:
(a) form liquid crystalline polymers by batching, described batching comprises the aliphatic diester of one or more first dicarboxylic acid, one or more first glycol and the aliphatic ester of one or more hydroxycarboxylic acids randomly; Then
(b) make described liquid crystalline polymers and every kilogram of described liquid crystalline polymers 2～200 millinormal second dicarboxylic acid contact for some time being enough to cause under the temperature of second dicarboxylic acid and described liquid crystalline polymers reaction, it is enough to make the tensile elongation increase at least 10% of described liquid crystalline polymers;
Condition is that the mol ratio of total amount of first dicarboxylic acid of the total amount of aliphatic diester of first glycol that exists in (a) and existence is 1.01 or bigger.
2. the process of claim 1 wherein that described mol ratio is 1.03～1.5.
3. claim 1 or 2 method, wherein there is millinormal second dicarboxylic acid of 5-50 in every kilogram of described liquid crystalline polymers.
4. claim 1 or 2 method, wherein said liquid crystalline polymers comprises the repeating unit that is derived from one or more following compounds: terephthalic acid, m-phthalic acid, 2,6-naphthalic acid, 4,4 '-diphenic acid and 1,8-naphthalic acid, ethylene glycol, quinhydrones, Resorcinol, 4,4 '-xenol, 2,6-dihydroxy naphthlene, 1,8-dihydroxy naphthlene, bisphenol-A, bis-phenol-S, 4-hydroxy-benzoic acid, 6-hydroxyl-2-naphthoic acid and tertiary butyl-4-hydroxy phenylformic acid.
5. the method for claim 4, wherein said liquid crystalline polymers comprises the repeating unit that is derived from one or more following compounds: terephthalic acid, m-phthalic acid, 2,6-naphthalic acid, quinhydrones and 4,4 '-xenol, 4-hydroxy-benzoic acid and 6-hydroxyl-2-naphthoic acid.
6. claim 1 or 2 method, the aliphatic ester of wherein said hydroxycarboxylic acid or the aliphatic diester of described glycol are acetic ester.
7. the method for claim 6, wherein said aliphatic ester are that original position forms.
8. claim 1 or 2 method, wherein said second dicarboxylic acid is an aromatic dicarboxylic acid.
9. claim 1 or 2 method, wherein said second dicarboxylic acid is 2,6-naphthalic acid, m-phthalic acid, 4,4 '-in diphenic acid, 2-methyl terephthalic acid and the hexanodioic acid one or more.
10. claim 1 or 2 method, wherein said second dicarboxylic acid is terephthalic acid and 2, one or both in the 6-naphthalic acid.
11. the method for claim 1 or 2, wherein said tensile elongation increase at least 20%.
12. wherein also there is the difunctional compound of second type in the method for claim 1 or 2.
13. the method for claim 12, the difunctional compound of wherein said second type exists with the amount of 20～100mol% of described second dicarboxylic acid.
14. the method for claim 12, the difunctional compound of wherein said second type are glycol or water.
15. the method for claim 12, the difunctional compound of wherein said second type is a water.
16. being the forms with hydrate, the method for claim 15, wherein said water exist.
17. the method for claim 16, wherein said hydrate is a hibbsite.
18. the method for claim 15, wherein the water yield of Cun Zaiing is 20～1000mol% based on the mole number of second dicarboxylic acid.
19. the formed formation of parts of making by the method for claim 1 of polymkeric substance.
20. the formed film of making by the method for claim 1 of polymkeric substance.
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|---|---|---|---|
| US50008703P | 2003-09-04 | 2003-09-04 | |
| US60/500,087 | 2003-09-04 | ||
| US60/537,539 | 2004-01-20 |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105143403A (en) * | 2013-03-13 | 2015-12-09 | 提克纳有限责任公司 | Liquid crystalline polymer composition |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4720424A (en) * | 1984-06-18 | 1988-01-19 | Hoebbst Celanese Corporation | Electronic component encapsulated with a composition comprising a polymer which is capable of forming an anisotropic melt phase and substantially incapable of further chain growth upon heating |
| US5672426A (en) * | 1994-06-20 | 1997-09-30 | Hoechst Celanese Corp | high barrier transparent films |
| US20020013424A1 (en) * | 1998-04-09 | 2002-01-31 | Soelch Richard Robert | Low viscosity liquid crystalline polymer compositions |
-
2004
- 2004-09-03 CN CNB2004800250904A patent/CN100415796C/en not_active Expired - Lifetime
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4720424A (en) * | 1984-06-18 | 1988-01-19 | Hoebbst Celanese Corporation | Electronic component encapsulated with a composition comprising a polymer which is capable of forming an anisotropic melt phase and substantially incapable of further chain growth upon heating |
| US5672426A (en) * | 1994-06-20 | 1997-09-30 | Hoechst Celanese Corp | high barrier transparent films |
| US20020013424A1 (en) * | 1998-04-09 | 2002-01-31 | Soelch Richard Robert | Low viscosity liquid crystalline polymer compositions |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105143403A (en) * | 2013-03-13 | 2015-12-09 | 提克纳有限责任公司 | Liquid crystalline polymer composition |
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