CN103483581A - Transparent polyamide and synthetic method thereof - Google Patents
Transparent polyamide and synthetic method thereof Download PDFInfo
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- CN103483581A CN103483581A CN201310430548.5A CN201310430548A CN103483581A CN 103483581 A CN103483581 A CN 103483581A CN 201310430548 A CN201310430548 A CN 201310430548A CN 103483581 A CN103483581 A CN 103483581A
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- diamine
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- 239000004952 Polyamide Substances 0.000 title claims abstract description 63
- 229920002647 polyamide Polymers 0.000 title claims abstract description 63
- 238000010189 synthetic method Methods 0.000 title description 4
- -1 hydrogen Chemical class 0.000 claims abstract description 25
- 229910052799 carbon Inorganic materials 0.000 claims abstract description 8
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 6
- 150000003839 salts Chemical class 0.000 claims description 58
- 238000002360 preparation method Methods 0.000 claims description 21
- 229920006020 amorphous polyamide Polymers 0.000 claims description 19
- 238000006243 chemical reaction Methods 0.000 claims description 14
- 150000004985 diamines Chemical class 0.000 claims description 14
- 150000001408 amides Chemical class 0.000 claims description 13
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical group CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 10
- KKEYFWRCBNTPAC-UHFFFAOYSA-N Terephthalic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-N 0.000 claims description 10
- 150000007520 diprotic acids Chemical class 0.000 claims description 10
- 239000003960 organic solvent Substances 0.000 claims description 10
- MQIUGAXCHLFZKX-UHFFFAOYSA-N Di-n-octyl phthalate Natural products CCCCCCCCOC(=O)C1=CC=CC=C1C(=O)OCCCCCCCC MQIUGAXCHLFZKX-UHFFFAOYSA-N 0.000 claims description 9
- 238000010792 warming Methods 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 5
- ROSDSFDQCJNGOL-UHFFFAOYSA-N Dimethylamine Chemical compound CNC ROSDSFDQCJNGOL-UHFFFAOYSA-N 0.000 claims description 4
- YZCKVEUIGOORGS-IGMARMGPSA-N Protium Chemical compound [1H] YZCKVEUIGOORGS-IGMARMGPSA-N 0.000 claims description 4
- 241000720974 Protium Species 0.000 claims description 4
- 229910021626 Tin(II) chloride Inorganic materials 0.000 claims description 4
- 238000001914 filtration Methods 0.000 claims description 4
- 239000003112 inhibitor Substances 0.000 claims description 4
- 229940045641 monobasic sodium phosphate Drugs 0.000 claims description 4
- 230000003647 oxidation Effects 0.000 claims description 4
- 238000007254 oxidation reaction Methods 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
- 238000004062 sedimentation Methods 0.000 claims description 4
- AJPJDKMHJJGVTQ-UHFFFAOYSA-M sodium dihydrogen phosphate Chemical compound [Na+].OP(O)([O-])=O AJPJDKMHJJGVTQ-UHFFFAOYSA-M 0.000 claims description 4
- 235000011150 stannous chloride Nutrition 0.000 claims description 4
- FDLQZKYLHJJBHD-UHFFFAOYSA-N [3-(aminomethyl)phenyl]methanamine Chemical compound NCC1=CC=CC(CN)=C1 FDLQZKYLHJJBHD-UHFFFAOYSA-N 0.000 claims description 2
- 230000015572 biosynthetic process Effects 0.000 claims description 2
- 238000007599 discharging Methods 0.000 claims description 2
- BNIILDVGGAEEIG-UHFFFAOYSA-L disodium hydrogen phosphate Chemical compound [Na+].[Na+].OP([O-])([O-])=O BNIILDVGGAEEIG-UHFFFAOYSA-L 0.000 claims description 2
- 229910000397 disodium phosphate Inorganic materials 0.000 claims description 2
- 235000019800 disodium phosphate Nutrition 0.000 claims description 2
- 229910000162 sodium phosphate Inorganic materials 0.000 claims description 2
- 239000001488 sodium phosphate Substances 0.000 claims description 2
- 235000011008 sodium phosphates Nutrition 0.000 claims description 2
- 238000003786 synthesis reaction Methods 0.000 claims description 2
- AXZWODMDQAVCJE-UHFFFAOYSA-L tin(II) chloride (anhydrous) Chemical compound [Cl-].[Cl-].[Sn+2] AXZWODMDQAVCJE-UHFFFAOYSA-L 0.000 claims description 2
- RYFMWSXOAZQYPI-UHFFFAOYSA-K trisodium phosphate Chemical compound [Na+].[Na+].[Na+].[O-]P([O-])([O-])=O RYFMWSXOAZQYPI-UHFFFAOYSA-K 0.000 claims description 2
- 239000001257 hydrogen Substances 0.000 abstract 2
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 abstract 1
- 150000001875 compounds Chemical class 0.000 abstract 1
- 125000004122 cyclic group Chemical group 0.000 abstract 1
- 229910052739 hydrogen Inorganic materials 0.000 abstract 1
- 238000001308 synthesis method Methods 0.000 abstract 1
- 238000012360 testing method Methods 0.000 description 10
- 239000004677 Nylon Substances 0.000 description 6
- 238000000338 in vitro Methods 0.000 description 6
- 238000000034 method Methods 0.000 description 6
- 229920001778 nylon Polymers 0.000 description 6
- 239000000203 mixture Substances 0.000 description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 5
- 239000002253 acid Substances 0.000 description 4
- 238000002844 melting Methods 0.000 description 4
- 230000008018 melting Effects 0.000 description 4
- 239000003595 mist Substances 0.000 description 4
- 239000002994 raw material Substances 0.000 description 4
- 238000011160 research Methods 0.000 description 4
- 229920002302 Nylon 6,6 Polymers 0.000 description 3
- 229920006351 engineering plastic Polymers 0.000 description 3
- SYECJBOWSGTPLU-UHFFFAOYSA-N hexane-1,1-diamine Chemical compound CCCCCC(N)N SYECJBOWSGTPLU-UHFFFAOYSA-N 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- 238000006068 polycondensation reaction Methods 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- 238000002834 transmittance Methods 0.000 description 3
- 238000001291 vacuum drying Methods 0.000 description 3
- TXUICONDJPYNPY-UHFFFAOYSA-N (1,10,13-trimethyl-3-oxo-4,5,6,7,8,9,11,12,14,15,16,17-dodecahydrocyclopenta[a]phenanthren-17-yl) heptanoate Chemical compound C1CC2CC(=O)C=C(C)C2(C)C2C1C1CCC(OC(=O)CCCCCC)C1(C)CC2 TXUICONDJPYNPY-UHFFFAOYSA-N 0.000 description 2
- 239000004743 Polypropylene Substances 0.000 description 2
- 125000001931 aliphatic group Chemical group 0.000 description 2
- 238000004458 analytical method Methods 0.000 description 2
- 229920001577 copolymer Polymers 0.000 description 2
- 238000013461 design Methods 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 239000004519 grease Substances 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 230000008676 import Effects 0.000 description 2
- 238000009413 insulation Methods 0.000 description 2
- 229920003023 plastic Polymers 0.000 description 2
- 238000006116 polymerization reaction Methods 0.000 description 2
- 239000001119 stannous chloride Substances 0.000 description 2
- 239000012780 transparent material Substances 0.000 description 2
- RNFJDJUURJAICM-UHFFFAOYSA-N 2,2,4,4,6,6-hexaphenoxy-1,3,5-triaza-2$l^{5},4$l^{5},6$l^{5}-triphosphacyclohexa-1,3,5-triene Chemical compound N=1P(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP=1(OC=1C=CC=CC=1)OC1=CC=CC=C1 RNFJDJUURJAICM-UHFFFAOYSA-N 0.000 description 1
- ZEMPKEQAKRGZGQ-AAKVHIHISA-N 2,3-bis[[(z)-12-hydroxyoctadec-9-enoyl]oxy]propyl (z)-12-hydroxyoctadec-9-enoate Chemical compound CCCCCCC(O)C\C=C/CCCCCCCC(=O)OCC(OC(=O)CCCCCCC\C=C/CC(O)CCCCCC)COC(=O)CCCCCCC\C=C/CC(O)CCCCCC ZEMPKEQAKRGZGQ-AAKVHIHISA-N 0.000 description 1
- KSMVBYPXNKCPAJ-UHFFFAOYSA-N 4-Methylcyclohexylamine Chemical compound CC1CCC(N)CC1 KSMVBYPXNKCPAJ-UHFFFAOYSA-N 0.000 description 1
- 241001044684 Amadina fasciata Species 0.000 description 1
- 241000196324 Embryophyta Species 0.000 description 1
- JHWNWJKBPDFINM-UHFFFAOYSA-N Laurolactam Chemical compound O=C1CCCCCCCCCCCN1 JHWNWJKBPDFINM-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- BJQHLKABXJIVAM-UHFFFAOYSA-N bis(2-ethylhexyl) phthalate Chemical compound CCCCC(CC)COC(=O)C1=CC=CC=C1C(=O)OCC(CC)CCCC BJQHLKABXJIVAM-UHFFFAOYSA-N 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 125000004432 carbon atom Chemical group C* 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 238000007334 copolymerization reaction Methods 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 230000002708 enhancing effect Effects 0.000 description 1
- JBKVHLHDHHXQEQ-UHFFFAOYSA-N epsilon-caprolactam Chemical compound O=C1CCCCCN1 JBKVHLHDHHXQEQ-UHFFFAOYSA-N 0.000 description 1
- 239000000945 filler Substances 0.000 description 1
- 238000011049 filling Methods 0.000 description 1
- 239000003063 flame retardant Substances 0.000 description 1
- 239000003365 glass fiber Substances 0.000 description 1
- 229920002521 macromolecule Polymers 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 230000035800 maturation Effects 0.000 description 1
- 239000000155 melt Substances 0.000 description 1
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 230000005622 photoelectricity Effects 0.000 description 1
- 229920006122 polyamide resin Polymers 0.000 description 1
- 229920000728 polyester Polymers 0.000 description 1
- 229920000573 polyethylene Polymers 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 229920001155 polypropylene Polymers 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 238000010561 standard procedure Methods 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- KUCOHFSKRZZVRO-UHFFFAOYSA-N terephthalaldehyde Chemical compound O=CC1=CC=C(C=O)C=C1 KUCOHFSKRZZVRO-UHFFFAOYSA-N 0.000 description 1
- 230000000930 thermomechanical effect Effects 0.000 description 1
- 229920001169 thermoplastic Polymers 0.000 description 1
- 239000004416 thermosoftening plastic Substances 0.000 description 1
Landscapes
- Polyamides (AREA)
Abstract
The invention discloses a transparent polyamide and a synthesis method thereof, wherein the polyamide has good transparency and wear resistance. The transparent polyamide of the invention has the following structural formula I:wherein: r1Represented by polymethylene- (CH)2)aA is an integer between 6 and 10; r2Represented by polymethylene- (CH)2)bB is an integer of 4-10; r3The compound is a molecular group which is composed of carbon and hydrogen elements and contains a side group or a ring structure; r4Represented by a molecular group containing a pendant group or a cyclic structure, which may be bonded to R, formed by carbon or hydrogen3The same or different; x and y are integers, and the sum of x and y is between 150 and 250.
Description
Technical field
The present invention relates to its synthetic method of a kind of polymeric amide, more specifically to a kind of transparent polyamide and synthetic method thereof.
Background technology
Nylon (polymeric amide) is that to be applied to the earliest be also a kind of thermoplastic engineering plastic that Present Domestic is most widely used outward.It has good over-all properties, comprise mechanical property, thermotolerance, wearability, chemical proofing and self lubricity, and frictional coefficient is low, certain flame retardant resistance is arranged, be easy to processing, be suitable for by glass fibre and other filler filling enhancing modified, steady-state growth in the cut-throat competition with other engineering plastics for many years, its demand still occupy the first place of five large-engineering plastics so far always.In many application, special at some to the exigent occasion of the physical and mechanical properties of transparent material, general transparent material oneself through not meeting people's requirement, so be the research to transparent polyamide, especially more noticeable.
Transparent nylon belongs to special nylon, some external companies have launched research to this, and realized suitability for industrialized production, " Trogamid " T developed as Dynamid Nobel company, the PACP9/6 that Phillips petrodeum company develops, " Isonamid " PA-7030 that " Grilamid " TR-55 that EMS company develops and Dow Chemical company develop.And at home, less about the research of transparent nylon, start late, and suitability for industrialized production is blank especially, complete dependence on import, and the domestic market demand amount is large, and every annual requirement is more than 10000 tons, and mainly from external import, price is up to ten thousand yuan of 15-20.Therefore the transparent polyamide material that exploitation has independent intellectual property right, fill the domestic gaps, significant to the fast development of domestic relevant industries.
Tradition fatty polyamide (PA-46, PA-66, PA-610 etc.) occupies very important status in polyamide resin, and its output accounts for more than 90%, therefore no matter in output, range of application, or over-all properties and price equilibrium ratio, absolute predominance is arranged.In addition, from raw material, abundanter, industrial scale is large, technology maturation.If therefore in amorphous polyamide salt, mix fatty polyamide salt, can under the prerequisite that keeps its transparency, reduce costs, improve over-all properties.
The cyclic aliphatic diprotic acid can hinder the polyamide segment of synthesized and the motion of macromolecular chain, hinders its macromolecule crystallization, also can make its macromole keep certain snappiness.At present, considerably less with the bibliographical information of the synthetic transparent polyamide of cyclic aliphatic diprotic acid, almost do not have.The bibliographical information of amorphous polyamide salt and the copolymerization of traditional fatty polyamide salt is also considerably less, almost do not have.
About disclosed similar techniques has: the mixture that for patent US3847977, hexanolactam, two (4-aminocyclohexyl) methane and molar fraction are 50% above terephthalic acid and m-phthalic acid is raw material, through polycondensation, prepares transparence polymeric amide preferably.The shortcoming of this product is that water-intake rate is high, and with easily becoming blushing after boiling water treating.Take trimethylammonium hexanediamine (TMD) and terephthalic acid in patent US3962400 is raw material, and by batchwise polymerization method method technique, melt phase polycondensation makes the transparent polyamide of high molecular.Adopt laurolactam, 4 in patent EP2324672,4 '-diamino-3,3 '-dimethyl-dicyclohexyl methyl hydride, the m-phthalic acid that mol ratio is 95:5 and terephthaldehyde's acid mixture have synthesized the transparent polyamide with excellent optical property, thermomechanical property, dimensional stability.The aliphatics lactan that patent CN1092087 be take ring grease diamines, m-phthalic acid, terephthalic acid and contained at least 7 carbon atoms and be raw material, melt phase polycondensation obtains a kind of transparent polyamide of height chemical-resistant reagent.
There is following shortcoming in above prior art: only use in building-up process ring grease diamines and the branched aliphatic diamine that price is higher, thereby cost is higher.Simultaneously at present the high-performance transparent nylon is produced only for abroad, so exploitation has independent intellectual property right, transparent nylon that production cost is lower has important research and application value.
Summary of the invention:
The objective of the invention is to solve above-mentioned problems of the prior art with not enough, a kind of transparent polyamide is provided, this polymeric amide has the good transparency and wear resistance.
The present invention also provides the preparation method with this transparent polyamide, and the method is simple and convenient, and cost is lower.
The present invention is achieved by the following technical solutions:
Transparent polyamide of the present invention, it has the structural formula of following I:
Wherein:
R
1that represent is polymethylene-(CH
2)
a-, a is the integer between 6~10;
R
2that represent is polymethylene-(CH
2)
b-, b is the integer between 4~10;
R
3what represent is the molecular radical that contains side group or ring texture formed with carbon, protium;
R
4representative be the molecular radical that contains side group or ring texture formed with carbon, protium, can with R
3identical or different;
X and y are integer, and itself and x+y are between 150~250.
The preparation method of the transparent polyamide that the present invention is above-mentioned, it comprises the following steps:
(1) polyamide salt is synthetic:
1. amorphous polyamide salt is synthetic: by the diamine of equimolar ratio with mix after diprotic acid is dissolved in organic solvent, by the sedimentation and filtration of separating out, oven dry, make amorphous polyamide salt; If not the crystalline state polyamide salt can not be separated out, the evaporate to dryness organic solvent, salt out amorphous polyamide dry;
2. fatty polyamide salt is synthetic: by the aliphatic diamine of equimolar ratio with mix after diprotic acid is dissolved in organic solvent, by the sedimentation and filtration of separating out, oven dry, make fatty polyamide salt; If fatty polyamide salt can not be separated out, the evaporate to dryness organic solvent, salt out fatty polyamide dry;
(2) polymeric amide is synthetic: by 50~100 weight part amorphous polyamide salt, and 0~50 weight part fatty polyamide salt, 0.1~2 weight part catalyzer, 0.1~1 weight part oxidation inhibitor adds in reactor successively; The hybrid reaction system is warming up to 190~240 ℃ under the condition vacuumized, and is incubated 4~6h; Continue to keep subsequently its vacuum state, be warming up to 260 ℃~310 ℃, then be incubated discharging after 4~6h, make transparent polyamide.
The preparation method of transparent polyamide of the present invention, in the synthesis step that its further technical scheme is described amorphous polyamide salt, diamine is the diamine that contains unsymmetrical structure or the diamine that contains benzene ring structure, and described diprotic acid is the diprotic acid that contains ring texture; Further technical scheme is that the described diamine that contains unsymmetrical structure is the trimethylammonium hexanediamine; The described diamine that contains benzene ring structure is Ursol D, mphenylenediamine, p dimethylamine or m-xylene diamine; The described diprotic acid that contains ring texture is to cyclohexyl dioctyl phthalate, terephthalic acid or m-phthalic acid.
The preparation method of transparent polyamide of the present invention, its further technical scheme can also be that described fatty polyamide salt is one or more in polymeric amide-46 salt, polymeric amide-66 salt, polymeric amide-610 salt, polymeric amide-1010 salt.
The preparation method of transparent polyamide of the present invention, its further technical scheme can also be that described organic solvent is ethanol.
The preparation method of transparent polyamide of the present invention, its further technical scheme can also be that the catalyzer described in step (2) is one or more in sodium phosphate, sodium hydrogen phosphate, SODIUM PHOSPHATE, MONOBASIC.
The preparation method of transparent polyamide of the present invention, its further technical scheme can also be that the oxidation inhibitor described in step (2) is tin protochloride.
The reaction equation of this reaction is:
Compared with prior art the present invention has following beneficial effect:
1) aliphatic diamine used in the present invention and aliphatic dibasic acid all can be from oil or Viscotrol C, and cost is lower; 2) polymeric amide that the present invention makes has the good transparency, plants thus the film transmittance that polymeric amide prepares and can reach more than 80%, and mist degree can reach below 40%; 3) the polymeric amide hardness that the present invention makes except the good transparency also is better than traditional polythene PE for the preparation of the transparent plastics product, polypropylene PP, polyester PET etc., has improved the wear resistance of transparent plastics product; 4) in the present invention, the equipment for the preparation of transparent polyamide is simple, effectively reduces cost; 5) the preparation process continuous and compact of transparent polyamide in the present invention, effectively shortened polymerization cycle, improved working efficiency.
Embodiment
Transparency, be the WGW photoelectricity mist degree instrument that adopts Physical Optics Instrument FActory, Shanghai Precision Science Instrument Co., L to produce in an embodiment, by standard method of test GR/T2410-2008, undertaken.
Embodiment 1
The preparation method of transparent polyamide salt-polyamide 66 salt copolymer, its preparation process is:
(1) polyamide salt is synthetic:
1. amorphous polyamide salt is synthetic: take 8.609g(0.05mol) to the cyclohexyl dioctyl phthalate, be placed in the 250mL Erlenmeyer flask that 50ml alcohol is housed, the water-bath of Erlenmeyer flask being put into to 60 ℃ makes the cyclohexyl dioctyl phthalate is dissolved.Take in addition 7.915g(0.05mol) the trimethylammonium hexanediamine, be placed in the 250mL Erlenmeyer flask that 60ml alcohol is housed, the water-bath of Erlenmeyer flask being put into to 60 ℃ is dissolved the trimethylammonium hexanediamine.Subsequently the spirituous solution of trimethylammonium hexanediamine is poured in the spirituous solution to the cyclohexyl dioctyl phthalate, the vibration Erlenmeyer flask, salt out amorphous polyamide.During not heat release of reaction system, amorphous polyamide salt is filtered in bottle, be placed in the vacuum drying oven of 40 ℃ and dry.
2. polymeric amide-66 salt is synthetic: take 7.307g(0.05mol) hexanodioic acid, be placed in the 250mL Erlenmeyer flask that 50ml alcohol is housed, the water-bath of Erlenmeyer flask being put into to 60 ℃ is dissolved hexanodioic acid.Take in addition 5.815g(0.05mol) hexanediamine, be placed in the 250mL Erlenmeyer flask that 60ml alcohol is housed, the water-bath of Erlenmeyer flask being put into to 60 ℃ is dissolved hexanediamine.Subsequently the spirituous solution of hexanediamine is poured in the spirituous solution of own dioctyl phthalate, the vibration Erlenmeyer flask, salt out polymeric amide-66.During not heat release of reaction system, polymeric amide-66 salt is filtered in bottle, be placed in the vacuum drying oven of 40 ℃ and dry.
(2) polymeric amide is synthetic: by 2.7 gram amorphous polyamide salt, 0.3 gram polymeric amide-66 salt adds in test tube successively, adds subsequently 2 of the SODIUM PHOSPHATE, MONOBASIC of concentration 0.075g/mL, 1 of the stannous chloride solution of concentration 0.075g/mL.Test tube is evacuated to vacuum tightness is-0.095~-0.10MPa between, with post-heating test tube to 180 ℃, now, invisible spectro polyamide 66 salt starts melting reaction, emits a large amount of water vapour.The reaction liberated heat makes temperature of reaction system continue to rise, and reaches the fusing point (210 ℃) of transparent polyamide salt, the melting of transparent polyamide salt reaction.After the test tube inner salt all melts, regulate design temperature, make 230 ℃ of its insulations, pressurize-0.10MPa, 5h, generate the prepolymer of wax-like transparent polyamide salt-polyamide 66 salt copolymer in vitro.Afterwards, keep in vitro original vacuum tightness, and progressively heat up.When temperature rises to 270 ℃ of left and right, prepolymer starts to melt and reacts and emit a large amount of water vapour.Continue to be warming up to 300 ℃, be incubated 300 ℃, after pressurize-0.1MPa, 4h, still keep in vitro original vacuum tightness, reaction system is slowly cooled to room temperature, take out product.Its structure through result after phenetic analysis as scheme lower as shown in.The film transmittance of making through this polymeric amide can reach 88.0%, and mist degree can reach 39.0%.
Embodiment 2
The preparation method of transparent polyamide, its preparation process is:
(1) polyamide salt is synthetic:
Synthesizing of amorphous polyamide salt: take 8.609g(0.05mol) to the cyclohexyl dioctyl phthalate, be placed in the 250mL Erlenmeyer flask that 50ml alcohol is housed, the water-bath of Erlenmeyer flask being put into to 60 ℃ makes the cyclohexyl dioctyl phthalate is dissolved.Take in addition 7.915g(0.05mol) the trimethylammonium hexanediamine, be placed in the 250mL Erlenmeyer flask that 50ml alcohol is housed, the water-bath of Erlenmeyer flask being put into to 60 ℃ is dissolved the trimethylammonium hexanediamine.Subsequently the spirituous solution of trimethylammonium hexanediamine is poured in the spirituous solution to the cyclohexyl dioctyl phthalate, the vibration Erlenmeyer flask, salt out amorphous polyamide.During not heat release of reaction system, amorphous polyamide salt is filtered in bottle, be placed in the vacuum drying oven of 40 ℃ and dry.
(2) polymeric amide is synthetic: 3 gram transparent polyamide salt are added in test tube, add subsequently 2 of the SODIUM PHOSPHATE, MONOBASIC of concentration 0.075g/mL, 1 of the stannous chloride solution of concentration 0.075g/mL.Test tube is evacuated to vacuum tightness is-0.095~-0.10MPa between, with post-heating test tube to 210 ℃, the melting of transparent polyamide salt reaction in reactor, emit a large amount of water vapour, after the whole meltings of test tube inner salt, regulate design temperature, make 230 ℃ of its insulations, pressurize-0.10MPa, 5h, generate wax-like polyamide prepolymer polymers in vitro.Afterwards, keep in vitro original vacuum tightness, continue to heat up.When temperature rises to 270 ℃, prepolymer starts to melt and reacts and emit a large amount of water vapour.Continue to be warming up to 300 ℃, be incubated 300 ℃, after pressurize-0.1MPa, 4h, still keep in vitro original vacuum tightness, reaction system is slowly cooled to room temperature, break test tube into pieces, take out product.Its structure result after phenetic analysis is as follows.The film transmittance of making through this polymeric amide can reach 85.8%.Mist degree can reach 37.4%.
Claims (8)
1. a transparent polyamide is characterized in that having the structural formula of following I:
Wherein:
R
1that represent is polymethylene-(CH
2)
a-, a is the integer between 6~10;
R
2that represent is polymethylene-(CH
2)
b-, b is the integer between 4~10;
R
3what represent is the molecular radical that contains side group or ring texture formed with carbon, protium;
R
4representative be the molecular radical that contains side group or ring texture formed with carbon, protium, can with R
3identical or different;
X and y are integer, and itself and x+y are between 150~250.
2. the preparation method of transparent polyamide as claimed in claim 1 is characterized in that comprising the following steps:
(1) polyamide salt is synthetic:
1. amorphous polyamide salt is synthetic: by the diamine of equimolar ratio with mix after diprotic acid is dissolved in organic solvent, by the sedimentation and filtration of separating out, oven dry, make amorphous polyamide salt; If not the crystalline state polyamide salt can not be separated out, the evaporate to dryness organic solvent, salt out amorphous polyamide dry;
2. fatty polyamide salt is synthetic: by the aliphatic diamine of equimolar ratio with mix after diprotic acid is dissolved in organic solvent, by the sedimentation and filtration of separating out, oven dry, make fatty polyamide salt; If fatty polyamide salt can not be separated out, the evaporate to dryness organic solvent, salt out fatty polyamide dry;
(2) polymeric amide is synthetic: by 50~100 weight part amorphous polyamide salt, and 0~50 weight part fatty polyamide salt, 0.1~2 weight part catalyzer, 0.1~1 weight part oxidation inhibitor adds in reactor successively; The hybrid reaction system is warming up to 190~240 ℃ under the condition vacuumized, and is incubated 4~6h; Continue to keep subsequently its vacuum state, be warming up to 260 ℃~310 ℃, then be incubated discharging after 4~6h, make transparent polyamide.
3. the preparation method of transparent polyamide according to claim 2, it is characterized in that diamine in the synthesis step of described amorphous polyamide salt is the diamine that contains unsymmetrical structure or the diamine that contains benzene ring structure, described diprotic acid is the diprotic acid that contains ring texture.
4. the preparation method of transparent polyamide according to claim 3, is characterized in that the described diamine that contains unsymmetrical structure is the trimethylammonium hexanediamine; The described diamine that contains benzene ring structure is Ursol D, mphenylenediamine, p dimethylamine or m-xylene diamine; The described diprotic acid that contains ring texture is to cyclohexyl dioctyl phthalate, terephthalic acid or m-phthalic acid.
5. the preparation method of transparent polyamide according to claim 2, is characterized in that described fatty polyamide salt is one or more in polymeric amide-46 salt, polymeric amide-66 salt, polymeric amide-610 salt, polymeric amide-1010 salt.
6. the preparation method of transparent polyamide according to claim 2, is characterized in that described organic solvent is ethanol.
7. the preparation method of transparent polyamide according to claim 2, is characterized in that the catalyzer described in step (2) is one or more in sodium phosphate, sodium hydrogen phosphate, SODIUM PHOSPHATE, MONOBASIC.
8. the preparation method of transparent polyamide according to claim 2, is characterized in that the oxidation inhibitor described in step (2) is tin protochloride.
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CN111454448A (en) * | 2019-05-14 | 2020-07-28 | 住华科技股份有限公司 | Polyamide and method for producing same |
CN118580488A (en) * | 2024-08-07 | 2024-09-03 | 山东广垠新材料有限公司 | High-toughness copolymerized transparent polyamide and preparation method thereof |
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CN111454448A (en) * | 2019-05-14 | 2020-07-28 | 住华科技股份有限公司 | Polyamide and method for producing same |
CN111454448B (en) * | 2019-05-14 | 2023-03-28 | 住华科技股份有限公司 | Polyamide and method for producing same |
CN118580488A (en) * | 2024-08-07 | 2024-09-03 | 山东广垠新材料有限公司 | High-toughness copolymerized transparent polyamide and preparation method thereof |
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