CN113930058B - Low-temperature thermoplastic plate composition and preparation method thereof - Google Patents
Low-temperature thermoplastic plate composition and preparation method thereof Download PDFInfo
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- CN113930058B CN113930058B CN202111274878.0A CN202111274878A CN113930058B CN 113930058 B CN113930058 B CN 113930058B CN 202111274878 A CN202111274878 A CN 202111274878A CN 113930058 B CN113930058 B CN 113930058B
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- 229920001169 thermoplastic Polymers 0.000 title claims abstract description 79
- 239000004416 thermosoftening plastic Substances 0.000 title claims abstract description 79
- 239000000203 mixture Substances 0.000 title claims abstract description 60
- 238000002360 preparation method Methods 0.000 title claims description 20
- 239000007822 coupling agent Substances 0.000 claims abstract description 23
- 239000000463 material Substances 0.000 claims abstract description 18
- 239000011256 inorganic filler Substances 0.000 claims abstract description 15
- 229910003475 inorganic filler Inorganic materials 0.000 claims abstract description 15
- 238000004519 manufacturing process Methods 0.000 claims abstract description 5
- 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 76
- 239000000178 monomer Substances 0.000 claims description 76
- NIHNNTQXNPWCJQ-UHFFFAOYSA-N fluorene Chemical compound C1=CC=C2CC3=CC=CC=C3C2=C1 NIHNNTQXNPWCJQ-UHFFFAOYSA-N 0.000 claims description 52
- KJFMBFZCATUALV-UHFFFAOYSA-N phenolphthalein Chemical compound C1=CC(O)=CC=C1C1(C=2C=CC(O)=CC=2)C2=CC=CC=C2C(=O)O1 KJFMBFZCATUALV-UHFFFAOYSA-N 0.000 claims description 52
- LXEJRKJRKIFVNY-UHFFFAOYSA-N terephthaloyl chloride Chemical compound ClC(=O)C1=CC=C(C(Cl)=O)C=C1 LXEJRKJRKIFVNY-UHFFFAOYSA-N 0.000 claims description 31
- QIGBRXMKCJKVMJ-UHFFFAOYSA-N Hydroquinone Chemical compound OC1=CC=C(O)C=C1 QIGBRXMKCJKVMJ-UHFFFAOYSA-N 0.000 claims description 27
- 229930185605 Bisphenol Natural products 0.000 claims description 26
- FDQSRULYDNDXQB-UHFFFAOYSA-N benzene-1,3-dicarbonyl chloride Chemical compound ClC(=O)C1=CC=CC(C(Cl)=O)=C1 FDQSRULYDNDXQB-UHFFFAOYSA-N 0.000 claims description 22
- KLDXJTOLSGUMSJ-JGWLITMVSA-N Isosorbide Chemical compound O[C@@H]1CO[C@@H]2[C@@H](O)CO[C@@H]21 KLDXJTOLSGUMSJ-JGWLITMVSA-N 0.000 claims description 21
- 229960002479 isosorbide Drugs 0.000 claims description 21
- NZGQHKSLKRFZFL-UHFFFAOYSA-N 4-(4-hydroxyphenoxy)phenol Chemical compound C1=CC(O)=CC=C1OC1=CC=C(O)C=C1 NZGQHKSLKRFZFL-UHFFFAOYSA-N 0.000 claims description 18
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 claims description 18
- 238000002156 mixing Methods 0.000 claims description 17
- 239000003365 glass fiber Substances 0.000 claims description 16
- 229920001610 polycaprolactone Polymers 0.000 claims description 16
- 239000004632 polycaprolactone Substances 0.000 claims description 16
- 229920002635 polyurethane Polymers 0.000 claims description 16
- 239000004814 polyurethane Substances 0.000 claims description 16
- 238000012695 Interfacial polymerization Methods 0.000 claims description 15
- 239000006087 Silane Coupling Agent Substances 0.000 claims description 15
- 125000004203 4-hydroxyphenyl group Chemical group [H]OC1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 14
- FYXKZNLBZKRYSS-UHFFFAOYSA-N benzene-1,2-dicarbonyl chloride Chemical compound ClC(=O)C1=CC=CC=C1C(Cl)=O FYXKZNLBZKRYSS-UHFFFAOYSA-N 0.000 claims description 14
- VCCBEIPGXKNHFW-UHFFFAOYSA-N biphenyl-4,4'-diol Chemical group C1=CC(O)=CC=C1C1=CC=C(O)C=C1 VCCBEIPGXKNHFW-UHFFFAOYSA-N 0.000 claims description 13
- 238000000034 method Methods 0.000 claims description 12
- 229920000642 polymer Polymers 0.000 claims description 11
- FRASJONUBLZVQX-UHFFFAOYSA-N 1,4-dioxonaphthalene Natural products C1=CC=C2C(=O)C=CC(=O)C2=C1 FRASJONUBLZVQX-UHFFFAOYSA-N 0.000 claims description 10
- BOKGTLAJQHTOKE-UHFFFAOYSA-N 1,5-dihydroxynaphthalene Chemical compound C1=CC=C2C(O)=CC=CC2=C1O BOKGTLAJQHTOKE-UHFFFAOYSA-N 0.000 claims description 10
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 10
- 230000015572 biosynthetic process Effects 0.000 claims description 9
- 239000002105 nanoparticle Substances 0.000 claims description 8
- UHOVQNZJYSORNB-UHFFFAOYSA-N benzene Substances C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 claims description 6
- 239000002994 raw material Substances 0.000 claims description 6
- 239000004593 Epoxy Substances 0.000 claims description 5
- 239000000377 silicon dioxide Substances 0.000 claims description 5
- 238000000465 moulding Methods 0.000 claims description 4
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 3
- PMHQVHHXPFUNSP-UHFFFAOYSA-M copper(1+);methylsulfanylmethane;bromide Chemical compound Br[Cu].CSC PMHQVHHXPFUNSP-UHFFFAOYSA-M 0.000 claims description 3
- 230000008569 process Effects 0.000 claims description 3
- 150000001875 compounds Chemical class 0.000 claims description 2
- 239000011541 reaction mixture Substances 0.000 claims description 2
- 230000006835 compression Effects 0.000 claims 1
- 238000007906 compression Methods 0.000 claims 1
- 229920000587 hyperbranched polymer Polymers 0.000 abstract description 55
- 239000011159 matrix material Substances 0.000 abstract description 39
- 230000007334 memory performance Effects 0.000 abstract description 6
- 230000009286 beneficial effect Effects 0.000 abstract description 2
- 239000002085 irritant Substances 0.000 abstract description 2
- 231100000021 irritant Toxicity 0.000 abstract description 2
- 231100000252 nontoxic Toxicity 0.000 abstract description 2
- 230000003000 nontoxic effect Effects 0.000 abstract description 2
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 54
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical group [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 44
- HTZCNXWZYVXIMZ-UHFFFAOYSA-M benzyl(triethyl)azanium;chloride Chemical compound [Cl-].CC[N+](CC)(CC)CC1=CC=CC=C1 HTZCNXWZYVXIMZ-UHFFFAOYSA-M 0.000 description 38
- 239000000243 solution Substances 0.000 description 38
- 239000000047 product Substances 0.000 description 29
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 24
- NHGXDBSUJJNIRV-UHFFFAOYSA-M tetrabutylammonium chloride Chemical compound [Cl-].CCCC[N+](CCCC)(CCCC)CCCC NHGXDBSUJJNIRV-UHFFFAOYSA-M 0.000 description 24
- 239000008367 deionised water Substances 0.000 description 22
- 229910021641 deionized water Inorganic materials 0.000 description 22
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 22
- 238000003756 stirring Methods 0.000 description 20
- 229920001230 polyarylate Polymers 0.000 description 18
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 12
- 238000009835 boiling Methods 0.000 description 10
- 239000003054 catalyst Substances 0.000 description 10
- 238000001035 drying Methods 0.000 description 10
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- 238000005303 weighing Methods 0.000 description 10
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 8
- 239000008346 aqueous phase Substances 0.000 description 8
- 229910001873 dinitrogen Inorganic materials 0.000 description 8
- 150000003839 salts Chemical class 0.000 description 8
- 238000012360 testing method Methods 0.000 description 8
- 239000003444 phase transfer catalyst Substances 0.000 description 6
- 230000008901 benefit Effects 0.000 description 5
- 238000011084 recovery Methods 0.000 description 5
- 230000009471 action Effects 0.000 description 4
- 239000000654 additive Substances 0.000 description 4
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- 239000002131 composite material Substances 0.000 description 4
- 229910017053 inorganic salt Inorganic materials 0.000 description 4
- 239000000376 reactant Substances 0.000 description 4
- 230000035484 reaction time Effects 0.000 description 4
- JRMUNVKIHCOMHV-UHFFFAOYSA-M tetrabutylammonium bromide Chemical compound [Br-].CCCC[N+](CCCC)(CCCC)CCCC JRMUNVKIHCOMHV-UHFFFAOYSA-M 0.000 description 4
- 238000004566 IR spectroscopy Methods 0.000 description 3
- 238000006243 chemical reaction Methods 0.000 description 3
- 238000000748 compression moulding Methods 0.000 description 3
- SCYULBFZEHDVBN-UHFFFAOYSA-N 1,1-Dichloroethane Chemical compound CC(Cl)Cl SCYULBFZEHDVBN-UHFFFAOYSA-N 0.000 description 2
- 102100021202 Desmocollin-1 Human genes 0.000 description 2
- 101000968043 Homo sapiens Desmocollin-1 Proteins 0.000 description 2
- 101000880960 Homo sapiens Desmocollin-3 Proteins 0.000 description 2
- 239000007864 aqueous solution Substances 0.000 description 2
- UWCPYKQBIPYOLX-UHFFFAOYSA-N benzene-1,3,5-tricarbonyl chloride Chemical compound ClC(=O)C1=CC(C(Cl)=O)=CC(C(Cl)=O)=C1 UWCPYKQBIPYOLX-UHFFFAOYSA-N 0.000 description 2
- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 description 2
- 239000007795 chemical reaction product Substances 0.000 description 2
- 238000005034 decoration Methods 0.000 description 2
- ZUOUZKKEUPVFJK-UHFFFAOYSA-N diphenyl Chemical compound C1=CC=CC=C1C1=CC=CC=C1 ZUOUZKKEUPVFJK-UHFFFAOYSA-N 0.000 description 2
- 238000002474 experimental method Methods 0.000 description 2
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 2
- 230000006872 improvement Effects 0.000 description 2
- 238000002329 infrared spectrum Methods 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- 239000003960 organic solvent Substances 0.000 description 2
- 238000012545 processing Methods 0.000 description 2
- 229920005989 resin Polymers 0.000 description 2
- 239000011347 resin Substances 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- 238000005979 thermal decomposition reaction Methods 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
- RZPFVRFSYMUDJO-UHFFFAOYSA-N 2h-naphthalen-1-one Chemical compound C1=CC=C2C(=O)CC=CC2=C1 RZPFVRFSYMUDJO-UHFFFAOYSA-N 0.000 description 1
- 206010067482 No adverse event Diseases 0.000 description 1
- 210000001015 abdomen Anatomy 0.000 description 1
- 150000001263 acyl chlorides Chemical class 0.000 description 1
- 125000002252 acyl group Chemical group 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- 239000012752 auxiliary agent Substances 0.000 description 1
- 235000010290 biphenyl Nutrition 0.000 description 1
- 239000004305 biphenyl Substances 0.000 description 1
- 238000006482 condensation reaction Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 239000003063 flame retardant Substances 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 125000000687 hydroquinonyl group Chemical group C1(O)=C(C=C(O)C=C1)* 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- 210000003141 lower extremity Anatomy 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 1
- 231100000956 nontoxicity Toxicity 0.000 description 1
- 229920000620 organic polymer Polymers 0.000 description 1
- 231100000915 pathological change Toxicity 0.000 description 1
- 230000036285 pathological change Effects 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- 239000004014 plasticizer Substances 0.000 description 1
- 239000002861 polymer material Substances 0.000 description 1
- 239000002952 polymeric resin Substances 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 230000003014 reinforcing effect Effects 0.000 description 1
- 239000012779 reinforcing material Substances 0.000 description 1
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- 125000000467 secondary amino group Chemical group [H]N([*:1])[*:2] 0.000 description 1
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Images
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L67/00—Compositions of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Compositions of derivatives of such polymers
- C08L67/04—Polyesters derived from hydroxycarboxylic acids, e.g. lactones
-
- 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
- C08G83/00—Macromolecular compounds not provided for in groups C08G2/00 - C08G81/00
- C08G83/002—Dendritic macromolecules
- C08G83/005—Hyperbranched macromolecules
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2201/00—Properties
- C08L2201/12—Shape memory
Abstract
The invention provides a low-temperature thermoplastic plate composition which is prepared from a base material, a hyperbranched polymer, an inorganic filler and a coupling agent. In the invention, the hyperbranched polymer is added into the low-temperature thermoplastic plate, wherein the hyperbranched polymer has good compatibility, processability and mechanical property with a matrix, can keep good shape memory property of the matrix material, endows the low-temperature thermoplastic plate with higher strength and realizes the use of the low-temperature thermoplastic plate in an environment with higher pressure. The prepared low-temperature thermoplastic plate has better shape memory performance, and is non-toxic and non-irritant. The process for preparing the low-temperature thermoplastic plate provided by the invention is simple and is beneficial to the realization of industrialization.
Description
Technical Field
The invention belongs to the technical field of polymers, and particularly relates to a low-temperature thermoplastic plate composition and a preparation method thereof.
Background
The low-temperature thermoplastic plate is a novel medical high polymer material, is clinically applied to the rehabilitation orthotics and the manufacturing of the orthotics, has the deformation temperature of 50-70 ℃, can be adjusted at any time according to needs, and is convenient to manufacture. According to market application survey of the Chinese (low-temperature thermoplastic plate) industry and research reports on feasibility of investment in 2017-2022, the scale of the rehabilitation medical market in 2022 is expected to reach more than one billion, and the usage amount of the low-temperature thermoplastic plate is expected to increase by 27.3% per year. Although the market of China is large, the market is basically limited to middle and low-end products, and high-end products are monopolized by foreign enterprises. The reason is that although the domestic low-temperature thermoplastic plate has better low-temperature shape memory performance, the material strength is obviously insufficient. It is not used in the environment with large stress such as lower limbs and spine, and is a restriction. Therefore, on the basis of maintaining the shape memory performance of the low-temperature thermoplastic plate material, the improvement of the strength of the material is a bottleneck problem which needs to be solved urgently.
The introduction of inorganic additives such as glass fibers (Composites Science and Technology,2012, 72. In addition, the inorganic additive has poor biocompatibility, and can cause skin-related pathological changes of patients after being contacted with human bodies for a long time. The introduction of high-performance organic polymer resin is an effective method for reinforcing materials, and has certain advantages compared with inorganic additives in the aspects of compatibility and biocompatibility with a matrix. However, the processing temperature of high-performance resin is generally higher, and the improvement of the processing performance is a key problem to be solved urgently.
Disclosure of Invention
In view of the above, the technical problem to be solved by the present invention is to provide a low temperature thermoplastic sheet composition and a preparation method thereof, wherein the hyperbranched polymer of the present invention has good compatibility, processability and mechanical properties with a matrix, can maintain good shape memory properties of the matrix material, endows the low temperature thermoplastic sheet with higher strength, and realizes the use of the low temperature thermoplastic sheet in an environment with higher pressure.
The invention provides a low-temperature thermoplastic plate composition which is prepared from a base material, a hyperbranched polymer, an inorganic filler and a coupling agent;
the hyperbranched polymer has a structure shown in a formula I and/or a formula II:
wherein Ar is formed 1 The monomer of the unit is selected from one or more of terephthaloyl chloride, isophthaloyl chloride and phthaloyl chloride;
formation of Ar 2 The monomer of the unit is selected from one or more of hydroquinone, phenolphthalein, bisphenol A, bisphenol fluorene, 4,4 '-dihydroxy diphenyl ether, 1,5-dihydroxy naphthalene, 4,4' -dihydroxy biphenyl and isosorbide
Formation of Ar 3 The monomer of the unit is selected from hydroquinone, phenolphthalein, bisphenol A, bisphenol fluorene, 4,4 '-dihydroxy diphenyl ether, 1,5-dihydroxy naphthalene, 4,4' -dihydroxy naphthaleneOne or more of biphenyl and isosorbide;
formation of Ar 4 The monomer of the unit is selected from one or more of terephthaloyl chloride, isophthaloyl chloride and phthaloyl chloride.
Preferably, the branching degree DB of the hyperbranched polyarylate is 0.1 to 0.8.
Preferably, the preparation method of the hyperbranched polymer having the structure shown in the formula I comprises the following steps:
carrying out interfacial polymerization on 3,3 (4-hydroxyphenyl) isobenzopyrrolidone, a diacyl chloride monomer and a dihydroxy monomer with a structure of a formula (III) to obtain hyperbranched polyarylate;
the bis-acyl chloride monomer is selected from one or more of terephthaloyl chloride, isophthaloyl chloride and phthaloyl chloride;
the dihydroxy monomer is selected from one or more of hydroquinone, phenolphthalein, bisphenol A, bisphenol fluorene, 4,4 '-dihydroxy diphenyl ether, 4,4' -dihydroxy diphenyl and isosorbide;
the preparation method of the hyperbranched polymer with the structure shown in the formula II comprises the following steps:
carrying out interfacial polymerization on 1,3,5-benzene tricarboxychloride monomer, diacyl chloride monomer and dihydroxyl monomer with the structure of formula (IV) to obtain hyperbranched polyarylate (II);
the bis-acyl chloride monomer is selected from one or more of terephthaloyl chloride, isophthaloyl chloride and phthaloyl chloride;
the dihydroxy monomer is selected from one or more of hydroquinone, phenolphthalein, bisphenol A, bisphenol fluorene, 4,4 '-dihydroxy diphenyl ether, 1,5-dihydroxy naphthalene, 4,4' -dihydroxy biphenyl and isosorbide.
Preferably, the matrix material is a blend of polyurethane and polycaprolactone, and the mass ratio of the polyurethane to the polycaprolactone is 5: 95-95: 5.
preferably, the inorganic filler is one or more of glass fiber, silica nanoparticles and aluminum nitride nanoparticles.
Preferably, the coupling agent is one or more of a titanate coupling agent, a silane coupling agent and an epoxy coupling agent.
Preferably, the preparation raw materials comprise:
100 parts by mass of a base material;
0.1 to 20 parts by mass of a hyperbranched polymer;
0 to 20 parts by mass of an inorganic filler;
0.01 to 2 parts by mass of a coupling agent.
The invention also provides a preparation method of the low-temperature thermoplastic plate, which is to mix the base material, the hyperbranched polymer, the inorganic filler and the coupling agent and then perform compression molding to obtain the low-temperature thermoplastic plate.
Preferably, the blending temperature is 100-300 ℃, and the time is 3-10 min.
Preferably, the temperature for compression molding is 50 to 300 ℃.
Compared with the prior art, the invention provides a low-temperature thermoplastic plate composition which is prepared from a base material, a hyperbranched polymer, an inorganic filler and a coupling agent. In the invention, the hyperbranched polymer is added into the low-temperature thermoplastic plate, wherein the hyperbranched polymer has good compatibility, processability and mechanical property with a matrix, can keep good shape memory property of the matrix material, endows the low-temperature thermoplastic plate with higher strength and realizes the use of the low-temperature thermoplastic plate in an environment with higher pressure. The prepared low-temperature thermoplastic plate has better shape memory performance, and is non-toxic and non-irritant. The process for preparing the low-temperature thermoplastic plate provided by the invention is simple and is beneficial to the realization of industrialization.
Drawings
FIG. 1 is a sheet appearance of a low temperature thermoplastic sheet prepared in example 1 of the present invention;
FIG. 2 is a photograph of a low temperature thermoplastic sheet after one week contact with the skin of a mouse;
FIG. 3 is an infrared spectrum of a hyperbranched polymer prepared in example 2;
FIG. 4 is an infrared spectrum of a hyperbranched polymer prepared in example 7.
Detailed Description
The invention provides a low-temperature thermoplastic plate composition which is prepared from a base material, a hyperbranched polymer, an inorganic filler and a coupling agent;
the hyperbranched polymer has a structure shown in formula I or formula II:
wherein Ar is formed 1 The monomer of the unit is selected from one or more of terephthaloyl chloride, isophthaloyl chloride and phthaloyl chloride; preferably one or more of terephthaloyl chloride and isophthaloyl chloride, more preferably terephthaloyl chloride or isophthaloyl chloride;
formation of Ar 2 The monomer of the unit is selected from one or more of hydroquinone, phenolphthalein, bisphenol A, bisphenol fluorene, 4,4 '-dihydroxy diphenyl ether, 1,5-dihydroxy naphthalene, 4,4' -dihydroxy biphenyl and isosorbide, preferably bisphenol A, phenolphthalein, bisphenol fluorene or isosorbide.
In the formula I, the compound is shown in the specification,
the groups representing the linkage to the Ar2 group are linked in the order Ar1, ar 2.
Formation of Ar 3 The monomer of the unit is selected from one or more of hydroquinone, phenolphthalein, bisphenol A, bisphenol fluorene, 4,4 '-dihydroxy diphenyl ether, 1,5-dihydroxy naphthalene, 4,4' -dihydroxy biphenyl and isosorbide; preferably one or more of bisphenol A, phenolphthalein, bisphenol fluorene and isosorbide, more preferably bisphenol A, phenolphthalein, bisphenol fluorene or isosorbide.
Formation of Ar 4 The monomer of the unit is selected from one or more of terephthaloyl chloride, isophthaloyl chloride and phthaloyl chloride; preferably one or more of terephthaloyl chloride and isophthaloyl chloride, more preferably terephthaloyl chlorideAcid chloride or isophthaloyl chloride.
In the formula II, the reaction mixture is shown in the specification,
represents a group linked to the Ar4 group, and Ar3 and Ar4 are linked in this order.
In the invention, the preparation method of the hyperbranched polymer with the structure shown in the formula I comprises the following steps:
carrying out interfacial polymerization on 3,3 (4-hydroxyphenyl) isobenzopyrrolidone, a diacyl chloride monomer and a dihydroxy monomer with a structure of a formula (III) to obtain hyperbranched polyarylate;
the bis-acyl chloride monomer is selected from one or more of terephthaloyl chloride, isophthaloyl chloride and phthaloyl chloride;
the dihydroxy monomer is selected from one or more of hydroquinone, phenolphthalein, bisphenol A, bisphenol fluorene, 4,4 '-dihydroxy diphenyl ether, 4,4' -dihydroxy diphenyl and isosorbide;
specifically, in the preparation process, in order to obtain the hyperbranched polyarylate with the structure described in the present application, the preparation process of the hyperbranched polyarylate specifically comprises:
reacting 3,3 (4-hydroxyphenyl) isobenzopyrrolidone with a dihydroxy monomer under the action of a catalyst and a phase transfer catalyst to obtain an initial reactant;
and dropwise adding the bisacyl chloride monomer solution into the initial reactant for reaction to obtain the hyperbranched polyarylate.
In the process, firstly, the dihydroxy monomer is activated by the catalyst, and then the dropwise added diacyl chloride monomer is added, so that on one hand, the dihydroxy monomer is used for adjusting the molecular weight and the structure, the addition amount is relatively small, and on the other hand, the solubility is relatively poor compared with that of the trifunctional monomer, and therefore, the conversion rate of the acyl chloride terminated trifunctional product obtained by reacting the dihydroxy monomer with the trifunctional monomer is high; and then, carrying out condensation reaction on the acyl chloride-terminated trifunctional product and a dihydroxy monomer to finally obtain the structure shown in the formula (I).
The bis-acyl chloride monomer is selected from one or more of terephthaloyl chloride, isophthaloyl chloride and phthaloyl chloride, and in particular embodiments, from one or both of terephthaloyl chloride and isophthaloyl chloride, and more preferably from one of terephthaloyl chloride and isophthaloyl chloride; the dihydroxy monomer is selected from one or more of hydroquinone, phenolphthalein, bisphenol A, bisphenol fluorene, 4,4 '-dihydroxy diphenyl ether, 1,5-dihydroxy naphthalene, 4,4' -dihydroxy biphenyl and isosorbide, preferably is one or more of phenolphthalein, bisphenol A, bisphenol fluorene, 4,4 '-dihydroxy diphenyl ether and isosorbide, and in the embodiment, is specifically selected from one of phenolphthalein, bisphenol A, bisphenol fluorene, 4,4' -dihydroxy diphenyl ether and isosorbide; the molar ratio of 3,3 (4-hydroxyphenyl) isobenzopyrrolidone, the diacyl chloride monomer and the dihydroxy monomer is 0.5-1: 2 to 6:2 to 6, in a particular embodiment, the molar ratio is between 0.5 and 0.8:2 to 5:2 to 5, more particularly 0.5 to 0.7:2 to 5:2 to 5.
Under the action of catalyst, the monomer is made into hyperbranched polyarylate through interfacial polymerization, wherein the catalyst is selected from NaOH and K 2 CO 3 And Na 2 CO 3 Preferably NaOH and Na 2 CO 3 One or two, more preferably NaOH; the phase transfer catalyst is selected from one or more of benzyl triethyl ammonium chloride (TEBAC), tetrabutyl ammonium chloride (TBAC) and tetrabutyl ammonium bromide (TBAB), preferably one or two of benzyl triethyl ammonium chloride (TEBAC) and tetrabutyl ammonium chloride (TBAC), more preferably one of benzyl triethyl ammonium chloride (TEBAC) and tetrabutyl ammonium chloride (TBAC).
The molar weight of the catalyst and the dihydroxy monomer is 2-10: 1, preferably 2 to 8:1, more specifically 2 to 6:1. the addition amount of the phase transfer catalyst is 0.2 to 10 percent, preferably 0.2 to 7 percent, and more particularly 0.2 to 5 percent of the total amount of the 3,3 (4-hydroxyphenyl) isobenzopyrrolidone, the diacyl chloride monomer and the dihydroxy monomer.
In the present application, the organic solvent of the bis-acyl chloride monomer solution in the interfacial polymerization is chloroform, dichloromethane or dichloroethane, preferably chloroform or dichloromethane, more preferably dichloromethane; the content of the solvent is 10 to 70 percent, preferably 35 to 65 percent, and more preferably 45 to 65 percent
The feeding method of the invention for the diacyl chloride monomer is a dropping method, the feeding rate is 0.01-30 ml/min, preferably 0.01-20 ml/min, in the embodiment, the accelerating rate is 0.01-5 ml/min; the interfacial polymerization temperature is-10 to 25 ℃, preferably-5 to 15 ℃, and in the embodiment, the interfacial polymerization temperature is specifically 0 to 10 ℃; the reaction time is 0.5 to 10 hours, preferably 2 to 8 hours, and in the examples, the reaction time is specifically 2.5 to 5 hours.
After the interfacial polymerization was stopped, the solution was precipitated in acetone under vigorous stirring, filtered, repeatedly boiled with deionized water and dried to give a white polymer product, which was analyzed by infrared spectroscopy. The thermal decomposition performance of the product was determined using a METTLER TOLEDO TGA/DSC1 thermogravimetric analyzer. Experiments show that the invention can prepare hyperbranched polyarylate with different structures, has good thermal stability and widens the application range of polyarylate.
In addition, the preparation method provided by the invention has the advantages of mild conditions, easiness in implementation, higher cost performance of the monomer, easiness in popularization and application and remarkable economic and social benefits.
In the invention, the preparation method of the hyperbranched polymer with the structure shown in the formula II comprises the following steps:
carrying out interfacial polymerization on 1,3,5-benzene tricarboxychloride monomer and dihydroxy monomer with the structure of formula (IV) to obtain hyperbranched polyarylate (II);
the bis-acyl chloride monomer is selected from one or more of terephthaloyl chloride, isophthaloyl chloride and phthaloyl chloride;
the dihydroxy monomer is selected from one or more of hydroquinone, phenolphthalein, bisphenol A, bisphenol fluorene, 4,4 '-dihydroxy diphenyl ether, 1,5-dihydroxy naphthalene (confirmed), 4,4' -dihydroxy biphenyl, and isosorbide.
Specifically, in the above preparation process, in order to obtain the hyperbranched polyarylate with the structure described in the present application, the preparation process of the hyperbranched polyarylate is specifically:
reacting 1,3,5-benzene tricarboxychloride monomer and dihydroxyl monomer under the action of catalyst and phase transfer catalyst to obtain initial reactant and dihydroxyl salt oligomer;
and dropwise adding the diacid chloride monomer solution into the initial reactant and the dihydroxyl salt oligomer to react to obtain the hyperbranched polyarylate.
In the process, firstly, the dihydroxyl monomer is activated by the catalyst, then the triacyl chloride monomer is dripped to obtain an initial product of the hydroxyl salt end capping, and then the initial product is condensed with the diacyl chloride monomer and then condensed with the hydroxyl salt monomer to obtain the structure shown in the formula (II).
The bis-acid chloride monomer is selected from one or more of terephthaloyl chloride, isophthaloyl chloride and phthaloyl chloride, and in particular embodiments, from one or two of terephthaloyl chloride and isophthaloyl chloride, and more preferably from one of terephthaloyl chloride and isophthaloyl chloride; the dihydroxy monomer is selected from one or more of hydroquinone, phenolphthalein, bisphenol A, bisphenol fluorene, 4,4 '-dihydroxy diphenyl ether, 1,5-dihydroxy naphthalene, 4,4' -dihydroxy biphenyl and isosorbide, preferably is one or more of phenolphthalein, bisphenol A, bisphenol fluorene, 4,4 '-dihydroxy diphenyl ether and isosorbide, and in the embodiment, is specifically selected from one of phenolphthalein, bisphenol A, bisphenol fluorene, 4,4' -dihydroxy diphenyl ether and isosorbide; the molar ratio of 1,3,5-benzene tricarboxychloride to the diacyl chloride monomer to the dihydroxyl monomer is 0.5-1: 2 to 6:2 to 6, in specific embodiments, the molar ratio is from 0.5 to 0.8:2 to 5:2 to 5, more particularly 0.5 to 0.7:2 to 5:2 to 5.
Under the action of catalyst, the above-mentioned monomer can be passed through the boundarySurface polymerization to obtain hyperbranched polyarylate, wherein the catalyst is selected from NaOH and K 2 CO 3 And Na 2 CO 3 Preferably NaOH and Na 2 CO 3 One or two, more preferably NaOH; the phase transfer catalyst is selected from one or more of benzyl triethyl ammonium chloride (TEBAC), tetrabutyl ammonium chloride (TBAC) and tetrabutyl ammonium bromide (TBAB), preferably one or two of benzyl triethyl ammonium chloride (TEBAC) and tetrabutyl ammonium chloride (TBAC), more preferably one of benzyl triethyl ammonium chloride (TEBAC) and tetrabutyl ammonium chloride (TBAC).
The molar weight of the catalyst and the dihydroxy monomer is 2-10: 1, preferably 2 to 8:1, more particularly 2 to 6:1. the dosage of the phase transfer catalyst is 0.2 to 10 percent of the total amount of the 1,3,5-benzene tricarboxychloride, the diacyl chloride monomer and the dihydroxyl monomer, preferably 0.2 to 7 percent, and more particularly 0.2 to 5 percent.
In the present application, the organic solvent of the diacyl chloride monomer solution in the interfacial polymerization is chloroform, dichloromethane or dichloroethane, preferably chloroform or dichloromethane, more preferably dichloromethane; the content of the solvent is 10 to 70 percent, preferably 35 to 65 percent, and more preferably 45 to 65 percent
The feeding method of the invention for the diacyl chloride monomer is a dropping method, the feeding rate is 0.01-30 ml/min, preferably 0.01-20 ml/min, in the embodiment, the accelerating rate is 0.01-5 ml/min; the interfacial polymerization temperature is-10 to 25 ℃, preferably-5 to 15 ℃, and in the embodiment, the interfacial polymerization temperature is specifically 0 to 10 ℃; the reaction time is 0.5 to 10 hours, preferably 2 to 8 hours, and in the examples, the reaction time is specifically 2.5 to 5 hours.
After the interfacial polymerization was stopped, the solution was precipitated in acetone under vigorous stirring, filtered, repeatedly washed with deionized water, dried to give a white polymer product, which was analyzed by infrared spectroscopy. The thermal decomposition performance of the product was determined by a METTLERTOLODO TGA/DSC1 thermogravimetric analyzer. Experiments show that the invention can prepare hyperbranched polyarylate with different structures, has good thermal stability and widens the application range of polyarylate.
In addition, the preparation method provided by the invention has the advantages of mild conditions, easiness in implementation, higher cost performance of the monomer, easiness in popularization and application and remarkable economic and social benefits.
In the present invention, the degree of branching DB of the hyperbranched polyarylate is 0.1 to 0.8, preferably 0.4 to 0.7, and more preferably 0.5 to 0.7.
The hyperbranched polymer has a highly branched topological structure, molecular chains are not entangled, a cavity structure is formed in the molecules, and the hyperbranched polymer contains a large number of end groups and endows the hyperbranched polymer with excellent functionality; meanwhile, the high-molecular main chain formed by the aromatic ring and the carbonyl group ensures that the mechanical stability of the composite material is excellent, the composite material has unique application in reinforcing resin auxiliaries, and the hyperbranched polymers with different structures are selected to reinforce the low-temperature thermoplastic plate, so that the application range of the composite material is widened.
In the invention, the matrix material is a blend of polyurethane and polycaprolactone, and the mass ratio of the polyurethane to the polycaprolactone is 5: 95-95: 5, preferably 40: 60-60: 40, more preferably 30: 70-70: 30, of a nitrogen-containing gas;
the inorganic filler is one or more of glass fiber, silica nanoparticles and aluminum nitride nanoparticles, preferably one or two of glass fiber and silica nanoparticles, and more preferably one of glass fiber and silica nanoparticles. In the invention, the inorganic filler can assist in improving the mechanical strength of the low-temperature thermoplastic plate
The coupling agent is one or more of titanate coupling agent, silane coupling agent and epoxy coupling agent, preferably one or two of silane coupling agent and epoxy coupling agent, and more preferably one of silane coupling agent and epoxy coupling agent. In the present invention, the coupling agent can improve the interaction between the matrices and other additives, thereby further improving the homogeneity and shape memory properties of the material.
The raw materials for preparing the low-temperature thermoplastic plate composition comprise 100 parts by mass of a base material;
the raw materials for preparing the low-temperature thermoplastic plate composition also comprise 0.1-20 parts by mass of hyperbranched polymer, preferably 0.1, 0.5, 1,5, 10, 15, 20 or 0.1-20 parts by mass;
the raw materials for preparing the low-temperature thermoplastic plate composition also comprise 0-20 parts by mass of inorganic filler, preferably 0, 0.1, 0.5, 1,5, 10, 15, 20 or any value between 0-20 parts by mass;
the raw materials for preparing the low-temperature thermoplastic plate composition also comprise 0.01-2 parts by mass of a coupling agent, preferably 0.01, 0.05, 0.1, 0.5, 1, 1.5, 2, or any value between 0.01-2 parts by mass.
In order to further improve the application performance of the low-temperature thermoplastic plate, the low-temperature thermoplastic plate composition can also comprise other auxiliary agents such as a flame retardant, a plasticizer and the like.
The invention also provides a preparation method of the low-temperature thermoplastic plate, which is to mix the base material, the hyperbranched polymer, the inorganic filler and the coupling agent and then perform compression molding to obtain the low-temperature thermoplastic plate.
The blending mode is not particularly limited in the present invention, and preferably an internal mixer is used for blending, the blending temperature is 100-300 ℃, preferably 100, 150, 200, 250, 300, or any value between 100-300 ℃, and the blending time is 3-10 min, preferably any value between 3,5, 7, 10, or any value between 3-10 min.
The molding method is not particularly limited in the present invention, and the press molding is preferably performed by a press vulcanizer, and the temperature for the press molding is 50 to 300 ℃, preferably 50, 100, 150, 200, 250, 300, or any value between 50 and 300 ℃.
After the low-temperature thermoplastic plate is processed and molded, the low-temperature thermoplastic plate is prepared into a standard sample strip for performance index testing.
The tensile property test is carried out according to the Chinese national standard GB/1040.2-2006, and the mechanical properties such as tensile strength, tensile modulus and the like are evaluated. The shape memory properties of the material, such as fixation rate, recovery rate and the like, are tested by a thermomechanical method.
The measurement result shows that the tensile strength of the low-temperature thermoplastic plate composition is 51MPa, the fixation rate is 90 percent, the recovery rate is 80 percent, and the low-temperature thermoplastic plate composition has good mechanical strength and shape memory performance.
In addition, the low-temperature thermoplastic plate provided by the invention has better mechanical strength and shape memory performance, and is lower in preparation cost, higher in cost performance and easy to popularize.
For further understanding of the present invention, the low temperature thermoplastic sheet composition and the method for preparing the same provided by the present invention are illustrated below with reference to the following examples, and the scope of the present invention is not limited by the following examples.
Example 1
In a three-necked flask equipped with a thermometer and charged with nitrogen gas, 3,3 (4-hydroxyphenyl) isobenzopyrrolidone (2.7 g), bisphenol A (3.2 g), naOH (1.5 g), benzyltriethylammonium chloride (0.27 g) and deionized water (50 ml) were charged and reacted at 10 ℃ for 1 hour. 30ml of dichloromethane solution dissolved with 3.6g of terephthaloyl chloride is added dropwise into the aqueous phase solution in the manner of 10min, the temperature is 10 ℃, and the stirring is carried out for 5h. Placing the solution in a beaker containing 50ml of acetone under vigorous stirring, precipitating for 2h, filtering, repeatedly boiling and washing with deionized water to remove residual inorganic salt, and drying to obtain a hyperbranched polymer white product with the branching degree of 0.4 and the yield of more than 90%.
Weighing 3g of the prepared hyperbranched polymer, wherein the mass ratio of the matrix material to the hyperbranched polymer is 15:1, wherein the mass ratio of polyurethane to polycaprolactone in the matrix material is 2:3, placing the mixture in an internal mixer for mixing at the temperature of 150 ℃ for 10min, then adding 0.2 percent of glass fiber and 0.1 percent of silane coupling agent based on the mass of the matrix to obtain a low-temperature thermoplastic plate composition, and carrying out mould pressing on the obtained composition by a flat vulcanizing machine at the temperature of 120 ℃ to obtain a low-temperature thermoplastic plate product.
Referring to fig. 1, fig. 1 shows the sheet appearance of the low temperature thermoplastic sheet prepared in example 1 of the present invention, and it can be seen from fig. 1 that the product appearance of the low temperature thermoplastic sheet is uniform.
Referring to fig. 2, fig. 2 shows that the low-temperature thermoplastic sheet is in contact with the skin of a mouse, specifically, the skin of the mouse is shaved, the material is made into a certain shape and is sleeved on the skin of the mouse, and the skin of the mouse has no adverse reaction for a week, as can be seen from fig. 2, the low-temperature thermoplastic sheet has no red swelling phenomenon after being in contact with the skin of the abdomen of the mouse for a week, and the low-temperature thermoplastic sheet prepared by the invention has no toxicity and no stimulation.
Example 2
In a three-necked flask equipped with a thermometer, charged with nitrogen gas and mechanically stirred, 2.7g of 3,3 (4-hydroxyphenyl) isobenzopyrrolidone, 4.9g of phenolphthalein, 1.5g of NaOH,0.27g of benzyltriethylammonium chloride, 50ml of deionized water were added and reacted at 10 ℃ for 1 hour. 30ml of dichloromethane solution dissolved with 3.6g of terephthaloyl chloride is added dropwise into the aqueous phase solution in the manner of 10min, the temperature is 10 ℃, and the stirring is carried out for 5h. Placing the solution in a beaker containing 50ml of acetone under vigorous stirring, precipitating for 2h, filtering, repeatedly boiling and washing with deionized water to remove residual inorganic salts, and drying to obtain a hyperbranched polymer white product with the branching degree of 0.44 and the yield of more than 90%.
Weighing 3g of the prepared hyperbranched polymer, wherein the mass ratio of the matrix material to the hyperbranched polymer is 15:1, wherein the mass ratio of polyurethane to polycaprolactone in the matrix material is 2:3, placing the mixture into an internal mixer for blending at 150 ℃ for 10min, and then adding 0.2 percent of glass fiber and 0.1 percent of silane coupling agent based on the mass of the matrix to obtain the low-temperature thermoplastic plate composition. And carrying out mould pressing on the obtained composition by a flat vulcanizing machine at 120 ℃ to obtain a low-temperature thermoplastic plate product.
Example 2 Infrared Spectroscopy as shown in FIG. 3, 3310cm -1 Is the secondary amine group vibration peak, 3177cm -1 Is the benzene ring C-H stretching vibration peak, 1653cm -1 1510cm as the peak of stretching vibration of carbonyl group -1 Is a stretching vibration peak of a benzene ring framework, which is 1244cm -1 Is the C-O-C stretching vibration peak.
And preparing sample bars with the same standard for performance index testing. The test result shows that the low-temperature thermoplastic plate has 53MPa of tensile strength, 251MPa of elastic modulus, 91 percent of fixation rate and 80 percent of recovery rate.
Example 3
In a three-necked flask equipped with a thermometer and charged with nitrogen gas, 3,3 (4-hydroxyphenyl) isobenzopyrrolidone (2.7 g), bisphenol fluorene (5.4 g), naOH (1.5 g), benzyltriethylammonium chloride (0.27 g) and deionized water (50 ml) were charged and reacted at 10 ℃ for 1 hour. 30ml of dichloromethane solution dissolved with 3.6g of terephthaloyl chloride is added dropwise into the aqueous phase solution in the manner of 10min, the temperature is 10 ℃, and the stirring is carried out for 5h. Placing the solution in a beaker containing 50ml of acetone under vigorous stirring, precipitating for 2h, filtering, repeatedly boiling and washing with deionized water to remove residual inorganic salt, and drying to obtain a hyperbranched polymer white product with the branching degree of 0.41 and the yield of more than 90%.
Weighing 3g of the prepared hyperbranched polymer, wherein the mass ratio of the matrix material to the hyperbranched polymer is 15:1, wherein the mass ratio of polyurethane to polycaprolactone in the matrix material is 2:3, placing the mixture in an internal mixer for blending at the temperature of 150 ℃ for 10min, and then adding 0.2 percent of glass fiber and 0.1 percent of silane coupling agent based on the mass of the matrix to obtain the low-temperature thermoplastic plate composition. And carrying out mould pressing on the obtained composition by a flat vulcanizing machine at 120 ℃ to obtain a low-temperature thermoplastic plate product.
Example 4
In a three-necked flask equipped with a thermometer, charged with nitrogen gas and mechanically stirred, 2.7g of 3,3 (4-hydroxyphenyl) isobenzopyrrolidone, 1.6g of bisphenol A,2.5g of phenolphthalein, 1.5g of NaOH,0.27g of benzyltriethylammonium chloride, 50ml of deionized water were charged and reacted at 10 ℃ for 1 hour. 30ml of dichloromethane solution dissolved with 3.6g of terephthaloyl chloride is added dropwise into the aqueous phase solution in the manner of 10min, the temperature is 10 ℃, and the stirring is carried out for 5h. Placing the solution in a beaker containing 50ml of acetone under vigorous stirring, precipitating for 2h, filtering, repeatedly boiling and washing with deionized water to remove residual inorganic salt, and drying to obtain a hyperbranched polymer white product with the branching degree of 0.45 and the yield of more than 90%.
Weighing 3g of the prepared hyperbranched polymer, wherein the mass ratio of the matrix material to the hyperbranched polymer is 15:1, wherein the mass ratio of polyurethane to polycaprolactone in the matrix material is 2:3, placing the mixture in an internal mixer for blending at the temperature of 150 ℃ for 10min, and then adding 0.2 percent of glass fiber and 0.1 percent of silane coupling agent based on the mass of the matrix to obtain the low-temperature thermoplastic plate composition. And carrying out mould pressing on the obtained composition by a flat vulcanizing machine at 120 ℃ to obtain a low-temperature thermoplastic plate product.
And preparing sample bars with the same standard for performance index testing. The test result shows that the low-temperature thermoplastic plate has the tensile strength of 51MPa, the elastic modulus of 243MPa, the fixing rate of 89 percent and the recovery rate of 81 percent.
Example 5
In a three-necked flask equipped with a thermometer, charged with nitrogen gas and mechanically stirred, 2.7g of 3,3 (4-hydroxyphenyl) isobenzopyrrolidone, 2.5g of phenolphthalein, 2.7g of bisphenol fluorene, 1.5g of NaOH,0.27g of benzyltriethylammonium chloride, 50ml of deionized water were added and reacted at 10 ℃ for 1 hour. 30ml of dichloromethane solution dissolved with 3.6g of terephthaloyl chloride is added dropwise into the aqueous phase solution in the manner of 10min, the temperature is 10 ℃, and the stirring is carried out for 5h. Placing the solution into a beaker filled with 50ml of acetone under vigorous stirring, precipitating for 2 hours, filtering, repeatedly boiling and washing with deionized water to remove residual inorganic salt, and drying to obtain a hyperbranched polymer white product with the yield of more than 90 percent.
Weighing 3g of the prepared hyperbranched polymer, wherein the mass ratio of the matrix material to the hyperbranched polymer is 15:1, wherein the mass ratio of polyurethane to polycaprolactone in the matrix material is 2:3, placing the mixture in an internal mixer for blending at the temperature of 150 ℃ for 10min, and then adding 0.2 percent of glass fiber and 0.1 percent of silane coupling agent based on the mass of the matrix to obtain the low-temperature thermoplastic plate composition. And carrying out mould pressing on the obtained composition by a flat vulcanizing machine at 120 ℃ to obtain a low-temperature thermoplastic plate product.
Example 6
In a three-necked flask equipped with a thermometer and charged with nitrogen gas and mechanically stirred, 2.7g of 3,3 (4-hydroxyphenyl) isobenzopyrrolidone, 1.6g of bisphenol A,2.7g of bisphenol fluorene, 1.5g of NaOH,0.27g of benzyltriethylammonium chloride, 50ml of deionized water were charged and reacted at 10 ℃ for 1 hour. 30ml of dichloromethane solution dissolved with 3.6g of terephthaloyl chloride is added dropwise into the aqueous phase solution in the manner of 10min, the temperature is 10 ℃, and the stirring is carried out for 5h. Placing the solution in a beaker containing 50ml of acetone under vigorous stirring, precipitating for 2h, filtering, repeatedly boiling and washing with deionized water to remove residual inorganic salts, and drying to obtain a white product of the hyperbranched polymer with the yield of more than 90%.
Weighing 3g of the prepared hyperbranched polymer, wherein the mass ratio of the matrix material to the hyperbranched polymer is 15:1, wherein the mass ratio of polyurethane to polycaprolactone in the matrix material is 2:3, placing the mixture in an internal mixer for blending at the temperature of 150 ℃ for 10min, and then adding 0.2 percent of glass fiber and 0.1 percent of silane coupling agent based on the mass of the matrix to obtain the low-temperature thermoplastic plate composition. And (3) carrying out mould pressing on the obtained composition by a flat vulcanizing machine at 120 ℃ to obtain a low-temperature thermoplastic plate product.
Example 7
5.6g of bisphenol fluorene, 1.5g of NaOH,0.27g of benzyltriethylammonium chloride and 50ml of deionized water were added into a mechanically stirred three-necked flask with a thermometer, nitrogen gas was introduced, and the mixture was reacted at 10 ℃ for 1 hour. 30ml of a solution of 1,3,5-benzenetricarbonyl chloride dissolved in 3.4g of dichloromethane were added dropwise to the aqueous solution over 10min, the temperature was 10 ℃ and the mixture was stirred for 3h. Then 30ml of dichloromethane solution dissolved with 3.7g of terephthaloyl chloride is added into the solution in a dropping mode for 10min, and the reaction is carried out for 3h. Placing the solution in a beaker containing 50ml of acetone under vigorous stirring, precipitating for 2h, filtering, repeatedly boiling and washing with deionized water to remove residual inorganic salts, and drying to obtain a hyperbranched polymer white product with a structure shown in an infrared spectrogram (figure 4), a branching degree of 0.4 and a yield of more than 90%.
Weighing 3g of the prepared hyperbranched polymer, wherein the mass ratio of the matrix material to the hyperbranched polymer is 15:1, wherein the mass ratio of polyurethane to polycaprolactone in the matrix material is 2:3, placing the mixture in an internal mixer for blending at the temperature of 150 ℃ for 10min, and then adding 0.2 percent of glass fiber and 0.1 percent of silane coupling agent based on the mass of the matrix to obtain the low-temperature thermoplastic plate composition. And carrying out mould pressing on the obtained composition by a flat vulcanizing machine at 120 ℃ to obtain a low-temperature thermoplastic plate product.
And preparing sample bars with the same standard for performance index testing. The test result shows that the low-temperature thermoplastic plate has the tensile strength of 43MPa, the elastic modulus of 206MPa, the fixation rate of 83 percent and the recovery rate of 81 percent.
Comparative example 1
In a three-necked flask equipped with a thermometer, charged with nitrogen gas and mechanically stirred, 2.7g of 3,3 (4-hydroxyphenyl) isobenzopyrrolidone, 4.9g of phenolphthalein, 1.5g of NaOH,0.27g of benzyltriethylammonium chloride, 50ml of deionized water were added and reacted at 10 ℃ for 1 hour. 30ml of dichloromethane solution dissolved with 3.6g of terephthaloyl chloride is added dropwise into the aqueous phase solution in the manner of 10min, the temperature is 10 ℃, and the stirring is carried out for 5h. Placing the solution in a beaker containing 50ml of acetone under vigorous stirring, precipitating for 2h, filtering, repeatedly boiling and washing with deionized water to remove residual inorganic salts, and drying to obtain a white product of the hyperbranched polymer with the yield of more than 90%.
Weighing 3g of the prepared hyperbranched polymer, wherein the mass ratio of the matrix material to the hyperbranched polymer is 30:1, wherein the mass ratio of polyurethane to polycaprolactone in the matrix material is 2:3, placing the mixture in an internal mixer for blending at 150 ℃ for 10min, and then adding 0.2 percent of glass fiber and 0.1 percent of silane coupling agent based on the mass of the matrix to obtain the low-temperature thermoplastic plate composition. And (3) carrying out mould pressing on the obtained composition by a flat vulcanizing machine at 120 ℃ to obtain a low-temperature thermoplastic plate product.
Comparative example 2
In a three-necked flask equipped with a thermometer, purged with nitrogen and mechanically stirred, 2.7g of 3,3 (4-hydroxyphenyl) isobenzopyrrolidone, 1.6g of bisphenol A,2.5g of phenolphthalein, 1.5g of NaOH,0.27g of benzyltriethylammonium chloride and 50ml of deionized water were charged and reacted at 30 ℃ for 1 hour. 30ml of dichloromethane solution dissolved with 3.6g of terephthaloyl chloride is added dropwise into the aqueous phase solution in the manner of 10min, the temperature is 30 ℃, and the stirring is carried out for 5h. Placing the solution in a beaker containing 50ml of acetone under vigorous stirring, precipitating for 2h, filtering, repeatedly boiling and washing with deionized water to remove residual inorganic salts, and drying to obtain a white product of the hyperbranched polymer with the yield of 40%.
Weighing 3g of the prepared hyperbranched polymer, wherein the mass ratio of the matrix material to the hyperbranched polymer is 15:1, wherein the mass ratio of polyurethane to polycaprolactone in the matrix material is 2:3, placing the mixture in an internal mixer for blending at the temperature of 150 ℃ for 10min, and then adding 0.2 percent of glass fiber and 0.1 percent of silane coupling agent based on the mass of the matrix to obtain the low-temperature thermoplastic plate composition. And carrying out mould pressing on the obtained composition by a flat vulcanizing machine at 120 ℃ to obtain a low-temperature thermoplastic plate product.
Comparative example 3
5.6g of bisphenol fluorene, 1.5g of NaOH,0.27g of benzyltriethylammonium chloride and 50ml of deionized water were added to a mechanically stirred three-necked flask with a thermometer and nitrogen, and the mixture was reacted at 10 ℃ for 1 hour. 30ml of a solution of 1,3,5-benzenetricarbonyl chloride in 3.4g of dichloromethane were added all at once to the above aqueous solution, the temperature was 10 ℃ and the mixture was stirred for 3 hours. 30ml of a methylene chloride solution containing 3.7g of terephthaloyl chloride was added to the above solution at once, and reacted for 3 hours. Placing the solution in a beaker containing 50ml of acetone under vigorous stirring, precipitating for 2h, filtering, repeatedly boiling and washing with deionized water to remove residual inorganic salts, and drying to obtain a white product of the hyperbranched polymer with the yield of 60%.
Weighing 3g of the prepared hyperbranched polymer, wherein the mass ratio of the matrix material to the hyperbranched polymer is 15:1, wherein the mass ratio of polyurethane to polycaprolactone in the matrix material is 2:3, placing the mixture in an internal mixer for blending at the temperature of 150 ℃ for 10min, and then adding 0.2 percent of glass fiber and 0.1 percent of silane coupling agent based on the mass of the matrix to obtain the low-temperature thermoplastic plate composition. And (3) carrying out mould pressing on the obtained composition by a flat vulcanizing machine at 120 ℃ to obtain a low-temperature thermoplastic plate product.
TABLE 1 Performance index for low temperature thermoplastic sheets of examples and comparative examples
As can be seen from Table 1, the low temperature thermoplastic sheet compositions provided by the embodiments of the present invention have good mechanical properties and shape memory properties, which are advantageous for applications.
The foregoing is only a preferred embodiment of the present invention, and it should be noted that, for those skilled in the art, various modifications and decorations can be made without departing from the principle of the present invention, and these modifications and decorations should also be regarded as the protection scope of the present invention.
Claims (8)
1. A low-temperature thermoplastic plate composition is characterized by being prepared from a base material, a polymer with a structure shown in a formula I and/or a formula II, an inorganic filler and a coupling agent;
the base material is a polyurethane and polycaprolactone blend, and the mass ratio of the polyurethane to the polycaprolactone is 5: 95-95: 5;
wherein Ar is formed 1 The monomer of the unit is selected from one or more of terephthaloyl chloride, isophthaloyl chloride and phthaloyl chloride;
formation of Ar 2 The monomer of the unit is selected from one or more of hydroquinone, phenolphthalein, bisphenol A, bisphenol fluorene, 4,4 '-dihydroxy diphenyl ether, 4,4' -dihydroxy diphenyl and isosorbide
Formation of Ar 3 The monomer of the unit is selected from one or more of hydroquinone, phenolphthalein, bisphenol A, bisphenol fluorene, 4,4 '-dihydroxy diphenyl ether, 1,5-dihydroxy naphthalene, 4,4' -dihydroxy biphenyl and isosorbide;
formation of Ar 4 The monomer of the unit is selected from one or more of terephthaloyl chloride, isophthaloyl chloride and phthaloyl chloride;
in the formula I, the compound is shown in the specification,
represents a group linked to an Ar2 group linked in order Ar1, ar 2;
in the formula II, the reaction mixture is shown in the formula II,
represents a group linked to an Ar4 group linked in order Ar3, ar 4;
the low-temperature thermoplastic plate composition is prepared from the following raw materials:
100 parts by mass of a base material;
0.1 to 20 parts by mass of a polymer having a structure represented by formula I and/or formula II;
0 to 20 parts by mass of an inorganic filler;
0.01 to 2 parts by mass of a coupling agent.
2. The composition according to claim 1, wherein the polymer having a structure according to formula I and/or formula II has a branching degree DB of 0.1 to 0.8.
3. The composition of claim 1, wherein the polymer having the structure of formula I is prepared by a process comprising the steps of:
carrying out interfacial polymerization on 3,3 (4-hydroxyphenyl) isobenzopyrrolidone, a diacyl chloride monomer and a dihydroxyl monomer with the structure of a formula (III) to obtain a polymer with the structure shown in a formula I;
the bis-acyl chloride monomer is selected from one or more of terephthaloyl chloride, isophthaloyl chloride and phthaloyl chloride;
the dihydroxy monomer is selected from one or more of hydroquinone, phenolphthalein, bisphenol A, bisphenol fluorene, 4,4 '-dihydroxy diphenyl ether, 4,4' -dihydroxy diphenyl and isosorbide;
the preparation method of the polymer with the structure shown in the formula II comprises the following steps:
carrying out interfacial polymerization on 1,3,5-benzene tricarboxychloride monomer, diacyl chloride monomer and dihydroxyl monomer with the structure of formula (IV) to obtain a polymer with the structure of formula II;
the bis-acyl chloride monomer is selected from one or more of terephthaloyl chloride, isophthaloyl chloride and phthaloyl chloride;
the dihydroxy monomer is selected from one or more of hydroquinone, phenolphthalein, bisphenol A, bisphenol fluorene, 4,4 '-dihydroxy diphenyl ether, 1,5-dihydroxy naphthalene, 4,4' -dihydroxy biphenyl and isosorbide.
4. The composition of claim 1, wherein the inorganic filler is one or more of glass fibers, silica nanoparticles, and aluminum nitride nanoparticles.
5. The composition of claim 1, wherein the coupling agent is one or more of a titanate coupling agent, a silane coupling agent, and an epoxy coupling agent.
6. A preparation method of a low-temperature thermoplastic plate is characterized in that a base material, the polymer with the structure shown in the formula I and/or the formula II in the claim 1, an inorganic filler and a coupling agent are blended and then are molded by compression to obtain the low-temperature thermoplastic plate.
7. The method according to claim 6, wherein the blending temperature is 100-300 ℃ and the blending time is 3-10 min.
8. The production method according to claim 6, wherein the temperature for the press molding is 50 to 300 ℃.
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB1196128A (en) * | 1966-10-11 | 1970-06-24 | Inst Elementoorganicheskikh So | Method of manufacturing Aromatic Polyesters |
| US5344910A (en) * | 1993-03-23 | 1994-09-06 | General Electric Company | Heat-resistant polycarbonate resins containing 2-alkyl-3,3-bis(p-hydroxyphenyl)phthalimide |
| CN1746206A (en) * | 2005-09-09 | 2006-03-15 | 浙江大学 | Copoaromatic ether and preparation thereof |
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| US7277230B2 (en) * | 2004-03-31 | 2007-10-02 | General Electric Company | Methods for producing and purifying 2-hydrocarbyl-3,3-bis(4-hydroxyaryl)phthalimidine monomers and polycarbonates derived therefrom |
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Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB1196128A (en) * | 1966-10-11 | 1970-06-24 | Inst Elementoorganicheskikh So | Method of manufacturing Aromatic Polyesters |
| US5344910A (en) * | 1993-03-23 | 1994-09-06 | General Electric Company | Heat-resistant polycarbonate resins containing 2-alkyl-3,3-bis(p-hydroxyphenyl)phthalimide |
| CN1746206A (en) * | 2005-09-09 | 2006-03-15 | 浙江大学 | Copoaromatic ether and preparation thereof |
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