CN100371363C - Resin material for formed article having profile cross section - Google Patents
Resin material for formed article having profile cross section Download PDFInfo
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- CN100371363C CN100371363C CNB2004800118328A CN200480011832A CN100371363C CN 100371363 C CN100371363 C CN 100371363C CN B2004800118328 A CNB2004800118328 A CN B2004800118328A CN 200480011832 A CN200480011832 A CN 200480011832A CN 100371363 C CN100371363 C CN 100371363C
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- polyacetal copolymer
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- 229920005989 resin Polymers 0.000 title claims abstract description 46
- 239000011347 resin Substances 0.000 title claims abstract description 46
- 239000000463 material Substances 0.000 title claims abstract description 30
- 229920006324 polyoxymethylene Polymers 0.000 claims abstract description 40
- 238000004519 manufacturing process Methods 0.000 claims abstract description 18
- 229920000642 polymer Polymers 0.000 claims abstract description 7
- 229930182556 Polyacetal Natural products 0.000 claims description 30
- 238000000034 method Methods 0.000 claims description 29
- 238000001125 extrusion Methods 0.000 claims description 25
- 238000000465 moulding Methods 0.000 claims description 25
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical group O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 claims description 13
- 125000002947 alkylene group Chemical group 0.000 claims description 9
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 4
- 125000000217 alkyl group Chemical group 0.000 claims description 4
- 229910052799 carbon Inorganic materials 0.000 claims description 4
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 4
- 238000004132 cross linking Methods 0.000 claims description 2
- 239000001257 hydrogen Substances 0.000 claims description 2
- 229910052739 hydrogen Inorganic materials 0.000 claims description 2
- 125000004435 hydrogen atom Chemical class [H]* 0.000 claims description 2
- -1 polyoxymethylene Polymers 0.000 abstract description 11
- 239000000155 melt Substances 0.000 abstract description 4
- 229930040373 Paraformaldehyde Natural products 0.000 abstract description 2
- 125000005704 oxymethylene group Chemical group [H]C([H])([*:2])O[*:1] 0.000 abstract 2
- 229920012196 Polyoxymethylene Copolymer Polymers 0.000 abstract 1
- 125000005702 oxyalkylene group Chemical group 0.000 abstract 1
- 230000000052 comparative effect Effects 0.000 description 15
- 238000007493 shaping process Methods 0.000 description 10
- 239000000203 mixture Substances 0.000 description 9
- NKDDWNXOKDWJAK-UHFFFAOYSA-N dimethoxymethane Chemical compound COCOC NKDDWNXOKDWJAK-UHFFFAOYSA-N 0.000 description 8
- 238000001816 cooling Methods 0.000 description 7
- 238000012545 processing Methods 0.000 description 7
- 239000000126 substance Substances 0.000 description 7
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 6
- 238000007334 copolymerization reaction Methods 0.000 description 6
- 238000006116 polymerization reaction Methods 0.000 description 6
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical group C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 5
- 239000012986 chain transfer agent Substances 0.000 description 5
- 238000011156 evaluation Methods 0.000 description 5
- 239000000178 monomer Substances 0.000 description 5
- 150000001335 aliphatic alkanes Chemical class 0.000 description 4
- 238000004458 analytical method Methods 0.000 description 4
- 150000001875 compounds Chemical class 0.000 description 4
- 238000002425 crystallisation Methods 0.000 description 4
- 230000008025 crystallization Effects 0.000 description 4
- 238000005516 engineering process Methods 0.000 description 4
- 238000005160 1H NMR spectroscopy Methods 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 description 3
- 239000002585 base Substances 0.000 description 3
- WERYXYBDKMZEQL-UHFFFAOYSA-N butane-1,4-diol Chemical compound OCCCCO WERYXYBDKMZEQL-UHFFFAOYSA-N 0.000 description 3
- 125000004122 cyclic group Chemical group 0.000 description 3
- 238000013461 design Methods 0.000 description 3
- 238000002156 mixing Methods 0.000 description 3
- 230000006641 stabilisation Effects 0.000 description 3
- 238000011105 stabilization Methods 0.000 description 3
- BYEAHWXPCBROCE-UHFFFAOYSA-N 1,1,1,3,3,3-hexafluoropropan-2-ol Chemical compound FC(F)(F)C(O)C(F)(F)F BYEAHWXPCBROCE-UHFFFAOYSA-N 0.000 description 2
- WNXJIVFYUVYPPR-UHFFFAOYSA-N 1,3-dioxolane Chemical compound C1COCO1 WNXJIVFYUVYPPR-UHFFFAOYSA-N 0.000 description 2
- XKTYXVDYIKIYJP-UHFFFAOYSA-N 3h-dioxole Chemical compound C1OOC=C1 XKTYXVDYIKIYJP-UHFFFAOYSA-N 0.000 description 2
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 2
- 229910052784 alkaline earth metal Inorganic materials 0.000 description 2
- 239000007864 aqueous solution Substances 0.000 description 2
- WTEOIRVLGSZEPR-UHFFFAOYSA-N boron trifluoride Chemical compound FB(F)F WTEOIRVLGSZEPR-UHFFFAOYSA-N 0.000 description 2
- 239000004566 building material Substances 0.000 description 2
- 238000012662 bulk polymerization Methods 0.000 description 2
- 239000003054 catalyst Substances 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 239000000460 chlorine Substances 0.000 description 2
- 229910052801 chlorine Inorganic materials 0.000 description 2
- 230000008602 contraction Effects 0.000 description 2
- 229920001577 copolymer Polymers 0.000 description 2
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 description 2
- 238000004090 dissolution Methods 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- FKRCODPIKNYEAC-UHFFFAOYSA-N ethyl propionate Chemical compound CCOC(=O)CC FKRCODPIKNYEAC-UHFFFAOYSA-N 0.000 description 2
- LYCAIKOWRPUZTN-UHFFFAOYSA-N ethylene glycol Natural products OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 2
- 238000005187 foaming Methods 0.000 description 2
- 230000004927 fusion Effects 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 239000012535 impurity Substances 0.000 description 2
- 238000002844 melting Methods 0.000 description 2
- 230000008018 melting Effects 0.000 description 2
- 230000000704 physical effect Effects 0.000 description 2
- 229920005672 polyolefin resin Polymers 0.000 description 2
- 239000004800 polyvinyl chloride Substances 0.000 description 2
- 229920000915 polyvinyl chloride Polymers 0.000 description 2
- 238000011002 quantification Methods 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 2
- 238000005406 washing Methods 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- LDXJRKWFNNFDSA-UHFFFAOYSA-N 2-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)-1-[4-[2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidin-5-yl]piperazin-1-yl]ethanone Chemical compound C1CN(CC2=NNN=C21)CC(=O)N3CCN(CC3)C4=CN=C(N=C4)NCC5=CC(=CC=C5)OC(F)(F)F LDXJRKWFNNFDSA-UHFFFAOYSA-N 0.000 description 1
- YSUQLAYJZDEMOT-UHFFFAOYSA-N 2-(butoxymethyl)oxirane Chemical compound CCCCOCC1CO1 YSUQLAYJZDEMOT-UHFFFAOYSA-N 0.000 description 1
- 229910015900 BF3 Inorganic materials 0.000 description 1
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical compound C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 description 1
- 229920000877 Melamine resin Polymers 0.000 description 1
- NIPNSKYNPDTRPC-UHFFFAOYSA-N N-[2-oxo-2-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)ethyl]-2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidine-5-carboxamide Chemical compound O=C(CNC(=O)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F)N1CC2=C(CC1)NN=N2 NIPNSKYNPDTRPC-UHFFFAOYSA-N 0.000 description 1
- ALQSHHUCVQOPAS-UHFFFAOYSA-N Pentane-1,5-diol Chemical compound OCCCCCO ALQSHHUCVQOPAS-UHFFFAOYSA-N 0.000 description 1
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 1
- 239000004698 Polyethylene Substances 0.000 description 1
- 239000004743 Polypropylene Substances 0.000 description 1
- GOOHAUXETOMSMM-UHFFFAOYSA-N Propylene oxide Chemical compound CC1CO1 GOOHAUXETOMSMM-UHFFFAOYSA-N 0.000 description 1
- AWMVMTVKBNGEAK-UHFFFAOYSA-N Styrene oxide Chemical compound C1OC1C1=CC=CC=C1 AWMVMTVKBNGEAK-UHFFFAOYSA-N 0.000 description 1
- DHKHKXVYLBGOIT-UHFFFAOYSA-N acetaldehyde Diethyl Acetal Natural products CCOC(C)OCC DHKHKXVYLBGOIT-UHFFFAOYSA-N 0.000 description 1
- 239000013543 active substance Substances 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 150000001342 alkaline earth metals Chemical class 0.000 description 1
- 238000005452 bending Methods 0.000 description 1
- 230000033228 biological regulation Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 125000002091 cationic group Chemical group 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 239000000470 constituent Substances 0.000 description 1
- 235000019628 coolness Nutrition 0.000 description 1
- 150000004292 cyclic ethers Chemical class 0.000 description 1
- 230000009849 deactivation Effects 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 238000007599 discharging Methods 0.000 description 1
- 239000000975 dye Substances 0.000 description 1
- 239000000796 flavoring agent Substances 0.000 description 1
- 235000019634 flavors Nutrition 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- XXMIOPMDWAUFGU-UHFFFAOYSA-N hexane-1,6-diol Chemical compound OCCCCCCO XXMIOPMDWAUFGU-UHFFFAOYSA-N 0.000 description 1
- 230000002779 inactivation Effects 0.000 description 1
- 239000003112 inhibitor Substances 0.000 description 1
- 238000001746 injection moulding Methods 0.000 description 1
- 238000009434 installation Methods 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 239000000314 lubricant Substances 0.000 description 1
- 238000003754 machining Methods 0.000 description 1
- JDSHMPZPIAZGSV-UHFFFAOYSA-N melamine Chemical compound NC1=NC(N)=NC(N)=N1 JDSHMPZPIAZGSV-UHFFFAOYSA-N 0.000 description 1
- 238000005457 optimization Methods 0.000 description 1
- 229920000620 organic polymer Polymers 0.000 description 1
- AHHWIHXENZJRFG-UHFFFAOYSA-N oxetane Chemical compound C1COC1 AHHWIHXENZJRFG-UHFFFAOYSA-N 0.000 description 1
- 239000000049 pigment Substances 0.000 description 1
- 229920000573 polyethylene Polymers 0.000 description 1
- 239000002861 polymer material Substances 0.000 description 1
- 230000000379 polymerizing effect Effects 0.000 description 1
- 229920001155 polypropylene Polymers 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 230000003068 static effect Effects 0.000 description 1
- 229920005992 thermoplastic resin Polymers 0.000 description 1
- ZIBGPFATKBEMQZ-UHFFFAOYSA-N triethylene glycol Chemical compound OCCOCCOCCO ZIBGPFATKBEMQZ-UHFFFAOYSA-N 0.000 description 1
- 230000000007 visual effect Effects 0.000 description 1
Images
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G2/00—Addition polymers of aldehydes or cyclic oligomers thereof or of ketones; Addition copolymers thereof with less than 50 molar percent of other substances
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L59/00—Compositions of polyacetals; Compositions of derivatives of polyacetals
- C08L59/04—Copolyoxymethylenes
Landscapes
- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Polyoxymethylene Polymers And Polymers With Carbon-To-Carbon Bonds (AREA)
- Compositions Of Macromolecular Compounds (AREA)
- Extrusion Moulding Of Plastics Or The Like (AREA)
- Polyethers (AREA)
Abstract
A resin material which comprises a polyoxymethylene copolymer having a polymer chain consisting mainly of an oxymethylene recurring unit and containing a specific oxyalkylene unit in an amount of 1.5 to 10 mol per 100 mol of the oxymethylene unit, and having a melt index (190 DEG C, a load of 2160g) of 0.3 to 20g/10 min, and is suitable for the production of a formed article having a profile cross section. The resin material allows the production of a formed article which comprises a polyoxymethylene resin and has a profile cross section, and further is reduced in strain and excellent in dimensional accuracy.
Description
Technical field
The present invention relates to comprise specific polyacetal copolymer, be suitable for being manufactured on the resin material and this moulding product that have the moulding product of good special crosssection shape when having excellent mechanical properties.
Background technology
As being technology, know special-shaped extrusion moulding with long products of complex cross-sectional shape with molding resin material.This abnormity extrusion moulding for example carries out as described below.Promptly, with extrusion shaping machine with resin material heating, fusion, mixing, extrude the die head of usefulness extrudes by the abnormity that is arranged on outlet of extruder, in typing cover that possesses stereotype plate, stock mould, tank etc. and cooling zone, be shaped as final cross-sectional shape on one side, make it cooling curing on one side, obtain special-shaped extrusion molding article as purpose.At this moment, by special-shaped shape or the calibrator of extruding with die head or typing die head of suitable change, can obtain the special-shaped extrusion molding article of all cross-sectional shapes.
Past, special-shaped extrusion molding article like this, most comprise polyvinyl chloride, but because polyvinyl chloride contains chlorine as constituent, therefore the problem that obnoxious flavour or the like takes place when burning is arranged, recently, the special-shaped extrusion molding article that comprises as the polyolefin-based resins of the polypropylene, polyethylene that do not contain the resin material of chlorine etc. becomes main flow.And, because these resin cheapnesss, so its special-shaped extrusion molding article is widely used in on a lot of purposes headed by the building materials.
, polyolefin-based resins is because crystallinity is low, so the intensity of its moulding product is limited, and the requirement in recent years more high-intensity special-shaped extrusion molding article often can not fully adapt to.
With respect to it, the polyformaldehyde resin that has mainly the polymer backbone that constitutes by the formaldehyde repeating unit, know the degree of crystallinity height, excellent on points such as rigidity, intensity, resistance to chemical reagents, solvent resistance, because its crystallization velocity is fast, shaping cycle is short, therefore is widely used mainly as the field of injection moulding material in the mechanism components of automobile, electric installation.
Like this, polyformaldehyde resin is the resin with excellent various characteristics, but polyformaldehyde resin is because the degree of crystallinity height, crystallization velocity is fast, therefore molding shrinkage is big etc., it is used for the occasion of special-shaped extrusion moulding, reduced cross-sectional takes place or the contraction during because of cooling curing deforms, thereby product deformation forms as the cross-sectional shape of purpose very difficult.
Therefore, use the extrusion moulding of polyformaldehyde resin abnormity almost not carry out in the past, in addition, the such proterties of polyformaldehyde resin in special-shaped extrusion moulding, the self property as described above that the polyformaldehyde resin that results from has, therefore its is improved to become and be suitable for special-shaped extrusion moulding and be considered to difficulty, almost not as the object of research.
As the prior art of the minority relevant, know that nib with ink runner extrudes forming composition (for example open clear 59-227498 communique with reference to the spy and the spy opens flat 8-142565 communique) with hollow with the special-shaped extrusion moulding of such polyformaldehyde resin.
The disclosed technology of these documents is the technology that has specificity on the material of the performance of having considered nib is selected, about the polyformaldehyde resin material of the extrusion moulding of the big special-shaped material of the special-shaped material that can be applicable to special-shaped extrusion moulding, particularly cross-sectional shape complexity especially effectively or sectional area, what is all unexposed.
Summary of the invention
The objective of the invention is to, solve above-mentioned problem, provide and to make the resin material that comprises polyacetal copolymer that is out of shape the special crosssection moulding product little, that dimensional precision is excellent in excellent in efficiency ground.
The inventor achieves the above object and found that of lucubrate, the resin material that comprises the specific polyacetal copolymer of having controlled crystallization velocity by use, obtaining abnormity, to extrude processibility good, the moulding product of the excellence that shaping and deformation is few, thus finish the present invention.
Promptly, the invention provides a kind of resin material that is suitable for making moulding product with special crosssection, it comprises polyacetal copolymer, and this polyacetal copolymer is the alkylene oxide unit, melt index (190 ℃, load 2160g) of the following general formula of usefulness (1) expression that to contain every 100mol formaldehyde unit in the polymer chain that mainly is made of the formaldehyde repeating unit the be 1.5-10mol multipolymer for the 0.3-20g/10 branch.
(in the formula, R
1, R
2From the alkyl of hydrogen, carbon number 1-8, the organic radical with alkyl of carbon number 1-8, phenyl, have the organic radical of phenyl and select R
1, R
2Can be the same or different.M represents the integer of 2-6.)
In addition, the present invention also provides the moulding product with special crosssection that obtained by such resin material.The present invention also be provided for making above-mentioned resin material the moulding product with special crosssection purposes and comprise manufacture method with the moulding product with special crosssection of above-mentioned molding resin material.
The simple declaration of accompanying drawing
Fig. 1 is a sectional view of representing the shape of the die head that uses in an embodiment.
Fig. 2 is the figure of the shape of the Vacuum shaping cover representing to use in an embodiment, (a) is sectional view, (b) is side-view.
The embodiment of invention
Below describe the present invention in detail.
Resin material of the present invention is the material that comprises polyacetal copolymer, the alkylene oxide unit of the above-mentioned general formula of usefulness (1) expression that this polyacetal copolymer contains every 100mol formaldehyde unit in the polymer chain that mainly is made of the formaldehyde repeating unit be 1.5-10mol.
In the present invention in the polyacetal copolymer of Shi Yonging, ratio with the alkylene oxide unit of general formula (1) expression need be that every 100mol formaldehyde unit is 1.5-10mol, preferred every 100mol formaldehyde unit is 2-8mol, and preferred especially every 100mol formaldehyde unit is 2-5mol.When the ratio of the alkylene oxide unit of representing with general formula (1) tails off, the crystallization velocity of polyacetal copolymer accelerates, when having the moulding product of special crosssection by the extrusion moulding manufacturing, the molten resin of extruding by extruder die head solidified be shaped as desired cross-sectional shape and cooling with the typing die head before, can not get desired shape.In addition, the curing speed that results from is fast, it is big that distortion in the forming composition that produces in the curing process becomes, and therefore becomes the shape of being out of shape sometimes.On the contrary, when increasing the ratio of the alkylene oxide unit of representing with general formula (1), the degree of crystallinity step-down of polyacetal copolymer, the moulding product that comprise such multipolymer become low moulding product such as intensity, Young's modulus.
In addition, the polyacetal copolymer of Shi Yonging in the present invention, the melt index of measuring under 190 ℃, the load of 2160g according to ASTM D-1238 (MI) is necessary for 0.3-20g/10 divides, preferably 0.5-10g/10 branch, especially preferably 0.5-5g/10 branch.When melt index (MI) is too small, melt extrude the load that adds man-hour and increase, extrude the difficulty that becomes, on the contrary, when melt index (MI) is excessive, because the contraction of resin etc. are made and become unstable.
The manufacture method of the above-mentioned polyacetal copolymer of Shi Yonging does not limit especially in the present invention, and usually available following method obtains: mainly use cationic polymerisation catalyst to make three alkane and as the cyclic ether compound or the mass polymerization of cyclic formals compound of comonomer.As poly-unit, known devices such as intermittent type, continous way all can use.Here, adjust according to the amount of the comonomer of copolymerization with the introducing ratio of the alkylene oxide unit of above-mentioned general formula (1) expression.In addition, melt index (MI) can be adjusted according to the addition of the chain-transfer agent that uses when the polymerization, for example methylal etc.
The melt index of resulting multipolymer diminishes once the addition that reduces chain-transfer agent, becomes big once the addition that increases chain-transfer agent.Moreover, for melt index, the kind of impurity such as contained water, methyl alcohol or polymerization machine, shape, size, polymerizing condition etc. also influence in starting monomer or the comonomer, therefore the decision absolute magnitude that obtains the necessary chain-transfer agent of multipolymer of specific melt index is difficult entirely, increase and decrease the addition of chain-transfer agent while the manufacturing of trying multipolymer, obtain the multipolymer of desired melt index.
The cyclic ether compound or the cyclic formals compound that use as comonomer, list oxyethane, propylene oxide, butylene oxide ring, Styrene oxide 98min., trimethylene oxide, tetrahydrofuran (THF), ト リ ォ キ セ パ Application, 1,3-dioxolane, propylene glycol formal, glycol ether formal, triglycol formal, 1,4-butyleneglycol formal, 1,5-pentanediol formal, 1,6-hexylene glycol formal etc., therein, optimization ethylene oxide, 1,3-dioxolane, glycol ether formal, 1,4-butyleneglycol formal.In addition, the polyacetal copolymer of Shi Yonging also can be the multipolymer with side chain or crosslinking structure in the present invention, for this reason, can be a small amount of multipolymer that adds the copolymerization such as glycidyl compound that simple function beyond above-mentioned or 2 officials can be above.
The polyacetal copolymer that obtains by polymerization, the inactivation that has carried out catalyzer is handled, after the stabilization treatment of the washing of the removal of unreacted monomer, polymkeric substance, drying, unstable terminal part etc., further, supply with practical by cooperating various stablizers to carry out stabilization treatment etc.As representational stablizer, can enumerate oxyhydroxide, inorganic acid salt, carboxylate salt of hindered phenol based compound, nitrogenous compound, alkali or alkaline-earth metal etc.
The polyacetal copolymer that obtains like this and use in the present invention adopts
1The terminal base unit weight of the detected hemiformal of H-NMR is 0-4mmol/kg, especially preferably 0-2mmol/kg preferably.Surpass the occasion of 4mmol/kg in the terminal base unit weight of hemiformal, the problem of the foaming of accompanying with the decomposition of polymkeric substance etc. takes place when melt-processed sometimes.For the terminal base unit weight of hemiformal is controlled at above-mentioned scope, preferably making for impurity, particularly moisture in polymeric monomer, the comonomer total amount is below the 20ppm, especially preferably below the 10ppm.
For the resin material that uses in the present invention, in such polyacetal copolymer, can add general additive as required, for example tinting material such as dyestuff, pigment, lubricant, nucleator, releasing agent, static inhibitor, tensio-active agent or organic polymer material, inorganic or organically fibrous, tabular, powder granulous weighting agent etc. more than a kind or 2 kinds in the scope of not damaging purpose of the present invention at thermoplastic resin.
The manufacture method of the moulding product with special crosssection that used the resin material that comprises above-mentioned polyacetal copolymer then, is described.Special-shaped extrusion moulding is used in manufacturing with moulding product of special crosssection usually.Have that the manufacturing of moulding product of special crosssection is following basically to be carried out like that.Promptly, be such method: after having the forcing machine internal heating molten resin of list or twin screw, extrusion moulding die head resin melt extrusion from shape with defined, in shaping process, be shaped as in the shape as purpose, make it to solidify and draw by refrigerating work procedure, cut into desired length as required, obtain the elongated formed body.At this, as the extrusion moulding die head, know straight die head, die head of right angle, flat die, special die head etc., select according to purpose.Except circle, also shaped design arbitrarily both can be and the similar shape of the cross-sectional shape of end article, also can be and its diverse cross-sectional shape with the shape (cross-sectional shape of the molten resin that is extruded) of die head in extrusion moulding.
In addition, in order to be shaped as the shape of purpose, the processing of in shaping process, finalizing the design from such molten resin that extrusion moulding is extruded with die head.As method for shaping, know outside typing method, inner typing method etc., but outside typing method is a main flow, therein, often utilizes the Vacuum shaping method.By the typing ornamenting resin of shape by curing that is cooled such as tank, water shower, air coolings, obtain goods as purpose.Cooling also can be carried out simultaneously with typing, also can be precooled to not solidified degree of molten resin before typing.
As resulting cross-sectional shape with moulding product of special crosssection, following shape all can: hollow shape, the hollow shape with ribbing that among hollow shape, is provided with rib, these shape blended compound shapes such as opening shape, cylinder, square tube such as L font, コ font, I shape, T font.
Moreover,, represented general gimmick here about the method for forming of moulding product with special crosssection, but the method for having used the manufacture method of the moulding product with special crosssection of resin material of the present invention to be not limited to put down in writing here.
The moulding product with special crosssection that use the resin material that comprises polyacetal copolymer of the present invention to obtain make full use of excellent characteristic such as its high strength, high elastic coefficient, solvent resistance, thermotolerance, bending fatigue resistance, have all purposes.Therefore machining object can be used according to suitable cut-out of purpose owing to be continuous morphology, for example can use in rail, pipe, various building materials, other all purposes.
Embodiment
Below adopt embodiment to specify the present invention, but the present invention is not limited thereto.
Embodiment 1-8
The use outside has the continous way hybrid reaction machine that the chuck, the cross section that lead to heat (cold) medium have the sleeve of 2 circular portion eclipsed shapes and be with the rotating shaft formation of paddle, on one side respectively with 2 rotating shafts of 150rpm rotating band paddle, add on one side three liquid alkane, as the cyclic ether or the cyclic formals of comonomer, supply with methylal continuously, also have catalyzer boron trifluoride 50ppm (with respect to whole unit) to carry out mass polymerization simultaneously to the polymerization machine on one side again as molecular weight regulator.Table 1 is expressed moisture content, the kind of comonomer, the methylal amount (with respect to the ratio of whole monomer weights) of three alkane of use.The amount of moisture of comonomer is below the 10ppm.Moreover, the target value of the melt index of resulting multipolymer, embodiment 1-3 and 5-7 are decided to be 2.0, and embodiment 4 is decided to be 1.5, and embodiment 8 is decided to be 9.0, has finely tuned the addition of methylal in the scope shown in the table 1.
The resultant of reaction of discharging from the polymerization machine leads to the pulverizer rapidly on one side, Yi Bian join in 60 ℃ the aqueous solution that contains 0.05 weight % triethylamine, with catalyst deactivation.And then after the separation, washing, drying, obtain thick polyacetal copolymer.Table 2 is expressed the proterties of resulting multipolymer.
Then, with respect to these thick polyacetal copolymer 100 weight parts, add the triethylamine 5 weight % aqueous solution 4 weight parts, tetramethylolmethane-four [3-(3, the 5-di-tert-butyl-hydroxy phenyl) propionic ester] 0.3 weight part, at 210 ℃ of melting mixings, remove l fraction with twin screw extruder.
To polyacetal copolymer 100 weight parts that obtain with aforesaid method, [3-(3 as the tetramethylolmethane-four of stablizer in interpolation, the 5-di-tert-butyl-hydroxy phenyl) propionic ester] 0.03 weight part and melamine 0.15 weight part, at 210 ℃ of melting mixings, obtain the resin material of partical with twin screw extruder.
Use the resin material of the above-mentioned partical that obtains, the extrusion shaping machine that adopts 200 ℃ of machine barrel design temperatures is with the resin fusion plastification, extrude from the die head (unit of the numeral the figure is mm) of cross-sectional shape shown in Figure 1, with while the cooling of reducing pressure resin being passed through in the brazen Vacuum shaping die head (unit of the numeral among the figure is mm) shown in Figure 2, obtain the forming composition of the rail shape of " コ word " type.Table 2 is expressed the result who estimates with evaluation assessment described later.
Comparative example 1-5
Except the amount or change methylal amount as shown in table 1 that change the comonomer that uses, similarly modulated outer polyoxymethylene (being total to) polymkeric substance of the regulation of the present invention shown in the table 2 with embodiment.Moreover, the target value of melt index, comparative example 1-3 is decided to be 2.0, and comparative example 4 is decided to be 27.0, has finely tuned the addition of methylal in the scope shown in the table 1.In addition, in comparative example 5,, do not carry out the interpolation of methylal in order to obtain the little multipolymer of melt index.
Resulting (being total to) polymkeric substance and embodiment are similarly carried out stabilization treatment etc., carry out abnormity again to extrude processing, obtain forming composition.Table 2 is expressed the result who estimates with evaluation assessment described later.
Embodiment 9
Except with 1, the 3-dioxolane carries out polymerization beyond together n-butyl glycidyl ether being added as copolymer composition similarly to Example 1, obtains having the thick polyacetal copolymer according to branched structure such shown in the table 3.After carrying out processing similarly to Example 1 again, enforcement has the manufacturing of the moulding product of special crosssection, obtains the forming composition of the rail shape of " コ word " type.Table 3 is expressed the result who estimates with evaluation assessment described later.
Moreover the metewand in the embodiment comparative example etc. are as follows.
[melt index (MI) mensuration]
Measure under 190 ℃, the load of 2160g according to ASIM D-1238.
[polymkeric substance compositional analysis]
The employed polymer dissolution of evaluation of physical property in hexafluoroisopropanol d2, is carried out
1H-NMR measures.By the peak area quantification corresponding with each unit.In table, use mol with respect to formaldehyde unit 100mol than the ratio of representing copolymerization units.
[terminal group analysis]
The employed polymer dissolution of evaluation of physical property in hexafluoroisopropanol d2, is carried out
1H-NMR measures.By the peak area quantification corresponding with each end.
[shape decision]
Whether visual observation becomes desired shape, judges with following benchmark.
3 minutes ... obtain desired cross-sectional shape.
2 minutes ... though roughly obtained desired cross section, can find a little distort or the surface concavo-convex.
1 minute ... can not get desired cross-sectional shape, can not process.
[forming process]
Judge that forming process has no problem.
Table 1
| Copolymer composition | Methylal amount (ppm) | |||
| Monomer (moisture content (ppm)) | Comonomer | |||
| Embodiment 1 | TOX | (13) | DO | 300～500 |
| |
TOX | (15) | DO | 300～500 |
| Embodiment 3 | TOX | (15) | DO | 300～500 |
| Embodiment 4 | TOX | (13) | DO | 300～500 |
| Embodiment 5 | TOX | (110) | DO | 300～500 |
| Embodiment 6 | TOX | (14) | BDF | 300～500 |
| Embodiment 7 | TOX | (13) | EGF | 300～500 |
| Embodiment 8 | TOX | (16) | DO | 500～800 |
| Comparative example 1 | TOX | (13) | DO | 300～500 |
| Comparative example 2 | TOX | (13) | DO | 300～500 |
| Comparative example 3 | TOX | (14) | - | 300～500 |
| Comparative example 4 | TOX | (14) | DO | 1000～1500 |
| Comparative example 5 | TOX | (13) | DO | 0 |
TOX: three alkane
DO:1, the 3-dioxolane
BDF:1,4-butyleneglycol formal
EGF: ethylene glycol acetal
Table 2
| The polymkeric substance compositional analysis is estimated | The judgement of forming composition and processibility | |||||
| Copolymerization units | mol | MI (g/10min) | Hemiformal (mmol/kg) | Shape decision | Forming process | |
| Embodiment 1 | (CH 2CH 2O) | 2.2 | 1.9 | 0.2 | 3 | Well |
| Embodiment 2 | (CH 2CH 2O) | 4.3 | 2.0 | 0.2 | 3 | Well |
| Embodiment 3 | (CH 2CH 2O) | 5.7 | 2.0 | 0.2 | 3 | Well |
| Embodiment 4 | (CH 2CH 2O) | 2.2 | 1.5 | 0.2 | 3 | Well |
| Embodiment 5 | (CH 2CH 2O) | 2.2 | 2.0 | 5 | 2 | Produce gas, a little foaming |
| Embodiment 6 | (CH 2CH 2CH 2CH 2O) | 2.2 | 2.1 | 0.2 | 3 | Well |
| Embodiment 7 | (CH 2CHO 2CH 2CH 2O) | 2.2 | 2.1 | 0.2 | 3 | Well |
| Embodiment 8 | (CH 2CH 2O) | 2.2 | 9 | 0.2 | 2 | Be low slightly viscosity, instability, but can process |
| Comparative example 1 | (CH 2CH 2O) | 1.2 | 2.2 | 0.2 | 1 | Processing difficulties |
| Comparative example 2 | (CH 2CH 2O) | 0.48 | 2 | 0.2 | 1 | Processing difficulties |
| Comparative example 3 | - | - | 2 | 0.2 | 1 | Processing difficulties |
| Comparative example 4 | (CH 2CH 2O) | 2.2 | 27 | 0.2 | 1 | Because so the resin low viscosity is processing difficulties |
| Comparative example 5 | (CH 2CH 2O) | 2.2 | 0.2 | 0.2 | 1 | Because the resin high viscosity is so the load of forcing machine is big |
Table 3
| The polymkeric substance compositional analysis is estimated | The judgement of forming composition and processibility | |||||||
| Copolymerization units-1 | mol | Copolymerization units-2 | mol | MI (g/10min) | Hemiformal (mmol/kg) | Shape decision | Forming process | |
| Embodiment 9 | (CH 2CH 2O) | 23 | (CH(CH 2OC 4H 8)CH 2O) | 0.25 | 1.9 | 0.2 | 3 | Well |
Claims (7)
1. manufacture method with moulding product of special crosssection, it comprises the step of special-shaped extrusion moulding resin material, wherein said resin material comprises polyacetal copolymer, the alkylene oxide unit of the following general formula of usefulness (1) expression that this polyacetal copolymer contains every 100mol formaldehyde unit in the polymer chain that mainly is made of the formaldehyde repeating unit be 1.5-10mol, melt index under 190 ℃, load 2160g is the 0.3-20g/10 branch
In the formula, R
1, R
2From the alkyl of hydrogen, carbon number 1-8, the organic radical with alkyl of carbon number 1-8, phenyl, have the organic radical of phenyl and select R
1, R
2Can be the same or different, m represents the integer of 2-6.
2. manufacture method according to claim 1, wherein, polyacetal copolymer is the multipolymer that contains the above-mentioned alkylene oxide unit of 2-8mol with respect to the 100mol formaldehyde unit.
3. manufacture method according to claim 1, wherein, polyacetal copolymer is the multipolymer that contains the above-mentioned alkylene oxide unit of 2-5mol with respect to the 100mol formaldehyde unit.
4. according to wantonly 1 described manufacture method of claim 1-3, wherein, polyacetal copolymer is the multipolymer with melt index of 0.5-10g/10 branch.
5. according to wantonly 1 described manufacture method of claim 1-3, wherein, polyacetal copolymer is the multipolymer with melt index of 0.5-5g/10 branch.
6. according to wantonly 1 described manufacture method of claim 1-3, wherein, polyacetal copolymer is the multipolymer with side chain or crosslinking structure.
7. according to wantonly 1 described manufacture method of claim 1-3, wherein, polyacetal copolymer is the multipolymer with hemiformal terminal group of 0-4mmol/kg.
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| JP5393016B2 (en) * | 2007-10-15 | 2014-01-22 | 宇部エクシモ株式会社 | Method for producing perforated tube |
Citations (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH09239856A (en) * | 1996-03-14 | 1997-09-16 | Asahi Chem Ind Co Ltd | Molding component of polyacetal resin |
| JPH09278983A (en) * | 1996-04-12 | 1997-10-28 | Polyplastics Co | Polyacetal resin composition and molded product thereof |
| JPH11279245A (en) * | 1998-03-30 | 1999-10-12 | Polyplastics Co | Production of polyacetal resin |
| US6037439A (en) * | 1997-08-22 | 2000-03-14 | Polyplastics Co., Ltd. | Process for continuous production of polyacetal resin |
| JP2000119357A (en) * | 1998-08-12 | 2000-04-25 | Asahi Chem Ind Co Ltd | Production of polyoxymethylene copolymer and polyoxymethylene copolymer composition |
| JP2000129080A (en) * | 1998-10-21 | 2000-05-09 | Asahi Chem Ind Co Ltd | Grafted polyoxymethylene resin |
| JP2000169668A (en) * | 1998-12-02 | 2000-06-20 | Polyplastics Co | Polyacetal resin composition and molded product obtained therefrom |
| JP2001089545A (en) * | 1999-09-24 | 2001-04-03 | Asahi Kasei Corp | Polyacetal resin molded article |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2004137415A (en) * | 2002-10-21 | 2004-05-13 | Mitsubishi Engineering Plastics Corp | Extrusion molded product made of polyacetal resin |
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2004
- 2004-04-30 WO PCT/JP2004/006327 patent/WO2004096881A1/en active Application Filing
- 2004-04-30 CN CNB2004800118328A patent/CN100371363C/en not_active Expired - Fee Related
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Patent Citations (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH09239856A (en) * | 1996-03-14 | 1997-09-16 | Asahi Chem Ind Co Ltd | Molding component of polyacetal resin |
| JPH09278983A (en) * | 1996-04-12 | 1997-10-28 | Polyplastics Co | Polyacetal resin composition and molded product thereof |
| US6037439A (en) * | 1997-08-22 | 2000-03-14 | Polyplastics Co., Ltd. | Process for continuous production of polyacetal resin |
| JPH11279245A (en) * | 1998-03-30 | 1999-10-12 | Polyplastics Co | Production of polyacetal resin |
| JP2000119357A (en) * | 1998-08-12 | 2000-04-25 | Asahi Chem Ind Co Ltd | Production of polyoxymethylene copolymer and polyoxymethylene copolymer composition |
| JP2000129080A (en) * | 1998-10-21 | 2000-05-09 | Asahi Chem Ind Co Ltd | Grafted polyoxymethylene resin |
| JP2000169668A (en) * | 1998-12-02 | 2000-06-20 | Polyplastics Co | Polyacetal resin composition and molded product obtained therefrom |
| JP2001089545A (en) * | 1999-09-24 | 2001-04-03 | Asahi Kasei Corp | Polyacetal resin molded article |
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| WO2004096881A1 (en) | 2004-11-11 |
| CN1784441A (en) | 2006-06-07 |
| JPWO2004096881A1 (en) | 2006-07-13 |
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