CN110563917A - Online modified PPC resin and preparation process thereof - Google Patents
Online modified PPC resin and preparation process thereof Download PDFInfo
- Publication number
- CN110563917A CN110563917A CN201911019341.2A CN201911019341A CN110563917A CN 110563917 A CN110563917 A CN 110563917A CN 201911019341 A CN201911019341 A CN 201911019341A CN 110563917 A CN110563917 A CN 110563917A
- Authority
- CN
- China
- Prior art keywords
- polyol
- parts
- mixture
- glycol
- ppc resin
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- 229920005989 resin Polymers 0.000 title claims abstract description 49
- 239000011347 resin Substances 0.000 title claims abstract description 49
- 238000002360 preparation method Methods 0.000 title claims abstract description 23
- 229920005862 polyol Polymers 0.000 claims abstract description 109
- 150000003077 polyols Chemical class 0.000 claims abstract description 106
- 239000000203 mixture Substances 0.000 claims abstract description 43
- -1 silicon polyol Chemical class 0.000 claims abstract description 37
- 239000004417 polycarbonate Substances 0.000 claims abstract description 32
- 239000003054 catalyst Substances 0.000 claims abstract description 31
- 229920000515 polycarbonate Polymers 0.000 claims abstract description 31
- 229920005906 polyester polyol Polymers 0.000 claims abstract description 22
- 150000002009 diols Chemical class 0.000 claims abstract description 21
- FBPFZTCFMRRESA-FSIIMWSLSA-N D-Glucitol Natural products OC[C@H](O)[C@H](O)[C@@H](O)[C@H](O)CO FBPFZTCFMRRESA-FSIIMWSLSA-N 0.000 claims abstract description 18
- FBPFZTCFMRRESA-JGWLITMVSA-N D-glucitol Chemical compound OC[C@H](O)[C@@H](O)[C@H](O)[C@H](O)CO FBPFZTCFMRRESA-JGWLITMVSA-N 0.000 claims abstract description 18
- 239000000600 sorbitol Substances 0.000 claims abstract description 18
- 239000012752 auxiliary agent Substances 0.000 claims abstract description 17
- SCPYDCQAZCOKTP-UHFFFAOYSA-N silanol Chemical compound [SiH3]O SCPYDCQAZCOKTP-UHFFFAOYSA-N 0.000 claims abstract description 17
- 229920001610 polycaprolactone Polymers 0.000 claims abstract description 16
- 239000004632 polycaprolactone Substances 0.000 claims abstract description 15
- 239000012948 isocyanate Substances 0.000 claims abstract description 14
- 150000002513 isocyanates Chemical class 0.000 claims abstract description 14
- 239000002994 raw material Substances 0.000 claims abstract description 12
- 229910052710 silicon Inorganic materials 0.000 claims abstract description 3
- 239000010703 silicon Substances 0.000 claims abstract description 3
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 37
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 claims description 21
- 229920000379 polypropylene carbonate Polymers 0.000 claims description 19
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 claims description 17
- WERYXYBDKMZEQL-UHFFFAOYSA-N butane-1,4-diol Chemical compound OCCCCO WERYXYBDKMZEQL-UHFFFAOYSA-N 0.000 claims description 16
- FPCJKVGGYOAWIZ-UHFFFAOYSA-N butan-1-ol;titanium Chemical compound [Ti].CCCCO.CCCCO.CCCCO.CCCCO FPCJKVGGYOAWIZ-UHFFFAOYSA-N 0.000 claims description 14
- 238000002156 mixing Methods 0.000 claims description 13
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 claims description 9
- PMMYEEVYMWASQN-IMJSIDKUSA-N cis-4-Hydroxy-L-proline Chemical compound O[C@@H]1CN[C@H](C(O)=O)C1 PMMYEEVYMWASQN-IMJSIDKUSA-N 0.000 claims description 9
- 238000001035 drying Methods 0.000 claims description 9
- XNGIFLGASWRNHJ-UHFFFAOYSA-N phthalic acid Chemical compound OC(=O)C1=CC=CC=C1C(O)=O XNGIFLGASWRNHJ-UHFFFAOYSA-N 0.000 claims description 9
- 229920001296 polysiloxane Polymers 0.000 claims description 8
- 238000005266 casting Methods 0.000 claims description 7
- 238000010438 heat treatment Methods 0.000 claims description 7
- 238000000034 method Methods 0.000 claims description 7
- 239000005058 Isophorone diisocyanate Substances 0.000 claims description 6
- 239000002202 Polyethylene glycol Substances 0.000 claims description 6
- NIMLQBUJDJZYEJ-UHFFFAOYSA-N isophorone diisocyanate Chemical compound CC1(C)CC(N=C=O)CC(C)(CN=C=O)C1 NIMLQBUJDJZYEJ-UHFFFAOYSA-N 0.000 claims description 6
- 229920001223 polyethylene glycol Polymers 0.000 claims description 6
- 239000004626 polylactic acid Substances 0.000 claims description 6
- 150000005846 sugar alcohols Polymers 0.000 claims description 6
- 229920000747 poly(lactic acid) Polymers 0.000 claims description 5
- 239000004629 polybutylene adipate terephthalate Substances 0.000 claims description 5
- DVKJHBMWWAPEIU-UHFFFAOYSA-N toluene 2,4-diisocyanate Chemical compound CC1=CC=C(N=C=O)C=C1N=C=O DVKJHBMWWAPEIU-UHFFFAOYSA-N 0.000 claims description 5
- UPMLOUAZCHDJJD-UHFFFAOYSA-N 4,4'-Diphenylmethane Diisocyanate Chemical compound C1=CC(N=C=O)=CC=C1CC1=CC=C(N=C=O)C=C1 UPMLOUAZCHDJJD-UHFFFAOYSA-N 0.000 claims description 4
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 claims description 4
- 229910052797 bismuth Inorganic materials 0.000 claims description 3
- JCXGWMGPZLAOME-UHFFFAOYSA-N bismuth atom Chemical compound [Bi] JCXGWMGPZLAOME-UHFFFAOYSA-N 0.000 claims description 3
- 230000008569 process Effects 0.000 claims description 3
- 239000005057 Hexamethylene diisocyanate Substances 0.000 claims description 2
- 229920002472 Starch Polymers 0.000 claims description 2
- WNLRTRBMVRJNCN-UHFFFAOYSA-L adipate(2-) Chemical compound [O-]C(=O)CCCCC([O-])=O WNLRTRBMVRJNCN-UHFFFAOYSA-L 0.000 claims description 2
- RNSLCHIAOHUARI-UHFFFAOYSA-N butane-1,4-diol;hexanedioic acid Chemical compound OCCCCO.OC(=O)CCCCC(O)=O RNSLCHIAOHUARI-UHFFFAOYSA-N 0.000 claims description 2
- 229910000019 calcium carbonate Inorganic materials 0.000 claims description 2
- 239000001913 cellulose Substances 0.000 claims description 2
- 229920002678 cellulose Polymers 0.000 claims description 2
- 239000002131 composite material Substances 0.000 claims description 2
- RRAMGCGOFNQTLD-UHFFFAOYSA-N hexamethylene diisocyanate Chemical compound O=C=NCCCCCCN=C=O RRAMGCGOFNQTLD-UHFFFAOYSA-N 0.000 claims description 2
- SLCVBVWXLSEKPL-UHFFFAOYSA-N neopentyl glycol Chemical compound OCC(C)(C)CO SLCVBVWXLSEKPL-UHFFFAOYSA-N 0.000 claims description 2
- 239000002667 nucleating agent Substances 0.000 claims description 2
- 239000004631 polybutylene succinate Substances 0.000 claims description 2
- 229920002961 polybutylene succinate Polymers 0.000 claims description 2
- 239000008107 starch Substances 0.000 claims description 2
- 235000019698 starch Nutrition 0.000 claims description 2
- 150000002148 esters Chemical class 0.000 claims 2
- 239000000454 talc Substances 0.000 claims 1
- 229910052623 talc Inorganic materials 0.000 claims 1
- 229920005630 polypropylene random copolymer Polymers 0.000 abstract description 52
- 238000006065 biodegradation reaction Methods 0.000 abstract description 6
- 238000005265 energy consumption Methods 0.000 abstract description 6
- 230000008901 benefit Effects 0.000 abstract description 3
- 229920005634 random propylene copolymer resin Polymers 0.000 abstract description 2
- 230000000052 comparative effect Effects 0.000 description 12
- 229920002635 polyurethane Polymers 0.000 description 12
- 239000004814 polyurethane Substances 0.000 description 12
- 229920002803 thermoplastic polyurethane Polymers 0.000 description 9
- 239000003795 chemical substances by application Substances 0.000 description 6
- 230000004048 modification Effects 0.000 description 6
- 238000012986 modification Methods 0.000 description 6
- 238000012360 testing method Methods 0.000 description 6
- 230000000694 effects Effects 0.000 description 5
- 229920003023 plastic Polymers 0.000 description 5
- 239000004033 plastic Substances 0.000 description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 5
- 239000011324 bead Substances 0.000 description 4
- 229910002092 carbon dioxide Inorganic materials 0.000 description 4
- FPAFDBFIGPHWGO-UHFFFAOYSA-N dioxosilane;oxomagnesium;hydrate Chemical compound O.[Mg]=O.[Mg]=O.[Mg]=O.O=[Si]=O.O=[Si]=O.O=[Si]=O.O=[Si]=O FPAFDBFIGPHWGO-UHFFFAOYSA-N 0.000 description 4
- 238000005187 foaming Methods 0.000 description 4
- 239000000047 product Substances 0.000 description 4
- 239000002002 slurry Substances 0.000 description 4
- HPGGPRDJHPYFRM-UHFFFAOYSA-J tin(iv) chloride Chemical compound Cl[Sn](Cl)(Cl)Cl HPGGPRDJHPYFRM-UHFFFAOYSA-J 0.000 description 4
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 3
- 239000004970 Chain extender Substances 0.000 description 3
- 239000004433 Thermoplastic polyurethane Substances 0.000 description 3
- 230000015556 catabolic process Effects 0.000 description 3
- 150000001875 compounds Chemical class 0.000 description 3
- 238000006731 degradation reaction Methods 0.000 description 3
- 125000005442 diisocyanate group Chemical group 0.000 description 3
- 229920001971 elastomer Polymers 0.000 description 3
- 239000000806 elastomer Substances 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- KJGLZJQPMKQFIK-UHFFFAOYSA-N methanolate;tributylstannanylium Chemical compound CCCC[Sn](CCCC)(CCCC)OC KJGLZJQPMKQFIK-UHFFFAOYSA-N 0.000 description 3
- 238000004806 packaging method and process Methods 0.000 description 3
- 239000004800 polyvinyl chloride Substances 0.000 description 3
- 229920000915 polyvinyl chloride Polymers 0.000 description 3
- KSBAEPSJVUENNK-UHFFFAOYSA-L tin(ii) 2-ethylhexanoate Chemical compound [Sn+2].CCCCC(CC)C([O-])=O.CCCCC(CC)C([O-])=O KSBAEPSJVUENNK-UHFFFAOYSA-L 0.000 description 3
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- 241000282414 Homo sapiens Species 0.000 description 2
- 230000009471 action Effects 0.000 description 2
- 230000004888 barrier function Effects 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 238000013329 compounding Methods 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 239000003208 petroleum Substances 0.000 description 2
- 239000013502 plastic waste Substances 0.000 description 2
- 229920003225 polyurethane elastomer Polymers 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- 241000894007 species Species 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- QLRYAXJYEVUQJU-UHFFFAOYSA-N (2-methylpropan-2-yl)oxytin Chemical compound CC(C)(C)O[Sn] QLRYAXJYEVUQJU-UHFFFAOYSA-N 0.000 description 1
- KMTRUDSVKNLOMY-UHFFFAOYSA-N Ethylene carbonate Chemical compound O=C1OCCO1 KMTRUDSVKNLOMY-UHFFFAOYSA-N 0.000 description 1
- 241000282412 Homo Species 0.000 description 1
- 239000004721 Polyphenylene oxide Substances 0.000 description 1
- GOOHAUXETOMSMM-UHFFFAOYSA-N Propylene oxide Chemical compound CC1CO1 GOOHAUXETOMSMM-UHFFFAOYSA-N 0.000 description 1
- 229910021623 Tin(IV) bromide Inorganic materials 0.000 description 1
- 229910021627 Tin(IV) chloride Inorganic materials 0.000 description 1
- 238000005299 abrasion Methods 0.000 description 1
- 230000002745 absorbent Effects 0.000 description 1
- 239000002250 absorbent Substances 0.000 description 1
- 239000006096 absorbing agent Substances 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- 239000002671 adjuvant Substances 0.000 description 1
- 125000003158 alcohol group Chemical group 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 229920003232 aliphatic polyester Polymers 0.000 description 1
- 229920001871 amorphous plastic Polymers 0.000 description 1
- 239000002518 antifoaming agent Substances 0.000 description 1
- 239000003963 antioxidant agent Substances 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 231100000209 biodegradability test Toxicity 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000001569 carbon dioxide Substances 0.000 description 1
- SIXOAUAWLZKQKX-UHFFFAOYSA-N carbonic acid;prop-1-ene Chemical compound CC=C.OC(O)=O SIXOAUAWLZKQKX-UHFFFAOYSA-N 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 238000009264 composting Methods 0.000 description 1
- 230000006835 compression Effects 0.000 description 1
- 238000007906 compression Methods 0.000 description 1
- 238000007334 copolymerization reaction Methods 0.000 description 1
- 239000007822 coupling agent Substances 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 229920006238 degradable plastic Polymers 0.000 description 1
- 239000008367 deionised water Substances 0.000 description 1
- 229910021641 deionized water Inorganic materials 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 239000002270 dispersing agent Substances 0.000 description 1
- 229920006351 engineering plastic Polymers 0.000 description 1
- 239000012467 final product Substances 0.000 description 1
- 239000003063 flame retardant Substances 0.000 description 1
- 239000004088 foaming agent Substances 0.000 description 1
- 235000013305 food Nutrition 0.000 description 1
- 239000002803 fossil fuel Substances 0.000 description 1
- 230000009477 glass transition Effects 0.000 description 1
- RXPAJWPEYBDXOG-UHFFFAOYSA-N hydron;methyl 4-methoxypyridine-2-carboxylate;chloride Chemical compound Cl.COC(=O)C1=CC(OC)=CC=N1 RXPAJWPEYBDXOG-UHFFFAOYSA-N 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 239000003112 inhibitor Substances 0.000 description 1
- IQPQWNKOIGAROB-UHFFFAOYSA-N isocyanate group Chemical group [N-]=C=O IQPQWNKOIGAROB-UHFFFAOYSA-N 0.000 description 1
- 239000012567 medical material Substances 0.000 description 1
- 238000010128 melt processing Methods 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 239000000178 monomer Substances 0.000 description 1
- 231100000956 nontoxicity Toxicity 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 230000035699 permeability Effects 0.000 description 1
- CSRCVZZUZZRSEH-UHFFFAOYSA-M phenoxytin Chemical compound [Sn]OC1=CC=CC=C1 CSRCVZZUZZRSEH-UHFFFAOYSA-M 0.000 description 1
- XNGIFLGASWRNHJ-UHFFFAOYSA-L phthalate(2-) Chemical compound [O-]C(=O)C1=CC=CC=C1C([O-])=O XNGIFLGASWRNHJ-UHFFFAOYSA-L 0.000 description 1
- 229920000570 polyether Polymers 0.000 description 1
- 229920000921 polyethylene adipate Polymers 0.000 description 1
- 229920002643 polyglutamic acid Polymers 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 229920000166 polytrimethylene carbonate Polymers 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- ULWHHBHJGPPBCO-UHFFFAOYSA-N propane-1,1-diol Chemical compound CCC(O)O ULWHHBHJGPPBCO-UHFFFAOYSA-N 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 229940116351 sebacate Drugs 0.000 description 1
- CXMXRPHRNRROMY-UHFFFAOYSA-L sebacate(2-) Chemical compound [O-]C(=O)CCCCCCCCC([O-])=O CXMXRPHRNRROMY-UHFFFAOYSA-L 0.000 description 1
- 230000035945 sensitivity Effects 0.000 description 1
- 239000003381 stabilizer Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 230000004083 survival effect Effects 0.000 description 1
- LTSUHJWLSNQKIP-UHFFFAOYSA-J tin(iv) bromide Chemical compound Br[Sn](Br)(Br)Br LTSUHJWLSNQKIP-UHFFFAOYSA-J 0.000 description 1
- 239000012780 transparent material Substances 0.000 description 1
- 238000010792 warming Methods 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/30—Low-molecular-weight compounds
- C08G18/32—Polyhydroxy compounds; Polyamines; Hydroxyamines
- C08G18/3203—Polyhydroxy compounds
- C08G18/3206—Polyhydroxy compounds aliphatic
-
- 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
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/30—Low-molecular-weight compounds
- C08G18/38—Low-molecular-weight compounds having heteroatoms other than oxygen
- C08G18/3893—Low-molecular-weight compounds having heteroatoms other than oxygen containing silicon
-
- 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
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/40—High-molecular-weight compounds
- C08G18/42—Polycondensates having carboxylic or carbonic ester groups in the main chain
- C08G18/4202—Two or more polyesters of different physical or chemical nature
-
- 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
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/40—High-molecular-weight compounds
- C08G18/42—Polycondensates having carboxylic or carbonic ester groups in the main chain
- C08G18/4205—Polycondensates having carboxylic or carbonic ester groups in the main chain containing cyclic groups
- C08G18/4208—Polycondensates having carboxylic or carbonic ester groups in the main chain containing cyclic groups containing aromatic groups
- C08G18/4211—Polycondensates having carboxylic or carbonic ester groups in the main chain containing cyclic groups containing aromatic groups derived from aromatic dicarboxylic acids and dialcohols
- C08G18/4216—Polycondensates having carboxylic or carbonic ester groups in the main chain containing cyclic groups containing aromatic groups derived from aromatic dicarboxylic acids and dialcohols from mixtures or combinations of aromatic dicarboxylic acids and aliphatic dicarboxylic acids and dialcohols
-
- 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
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/40—High-molecular-weight compounds
- C08G18/42—Polycondensates having carboxylic or carbonic ester groups in the main chain
- C08G18/4266—Polycondensates having carboxylic or carbonic ester groups in the main chain prepared from hydroxycarboxylic acids and/or lactones
- C08G18/4269—Lactones
- C08G18/4277—Caprolactone and/or substituted caprolactone
-
- 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
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/40—High-molecular-weight compounds
- C08G18/42—Polycondensates having carboxylic or carbonic ester groups in the main chain
- C08G18/4266—Polycondensates having carboxylic or carbonic ester groups in the main chain prepared from hydroxycarboxylic acids and/or lactones
- C08G18/428—Lactides
-
- 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
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/40—High-molecular-weight compounds
- C08G18/42—Polycondensates having carboxylic or carbonic ester groups in the main chain
- C08G18/44—Polycarbonates
-
- 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
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/65—Low-molecular-weight compounds having active hydrogen with high-molecular-weight compounds having active hydrogen
- C08G18/66—Compounds of groups C08G18/42, C08G18/48, or C08G18/52
- C08G18/6633—Compounds of group C08G18/42
- C08G18/6637—Compounds of group C08G18/42 with compounds of group C08G18/32 or polyamines of C08G18/38
- C08G18/664—Compounds of group C08G18/42 with compounds of group C08G18/32 or polyamines of C08G18/38 with compounds of group C08G18/3203
-
- 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
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/65—Low-molecular-weight compounds having active hydrogen with high-molecular-weight compounds having active hydrogen
- C08G18/66—Compounds of groups C08G18/42, C08G18/48, or C08G18/52
- C08G18/6633—Compounds of group C08G18/42
- C08G18/6637—Compounds of group C08G18/42 with compounds of group C08G18/32 or polyamines of C08G18/38
- C08G18/664—Compounds of group C08G18/42 with compounds of group C08G18/32 or polyamines of C08G18/38 with compounds of group C08G18/3203
- C08G18/6644—Compounds of group C08G18/42 with compounds of group C08G18/32 or polyamines of C08G18/38 with compounds of group C08G18/3203 having at least three hydroxy groups
-
- 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
- C08G2230/00—Compositions for preparing biodegradable polymers
Landscapes
- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Polyurethanes Or Polyureas (AREA)
Abstract
The invention relates to the technical field of PPC (polypropylene random copolymer) resin, in particular to an online modified PPC resin and a preparation process thereof, wherein the online modified PPC resin comprises the following raw materials in parts by weight: 100 parts of polyol, 15-60 parts of isocyanate, 2.4-17 parts of micromolecular diol, 0.1-0.2 part of catalyst, 3-10 parts of hydroxyl silane and 1-30 parts of auxiliary agent, wherein the polyol is a mixture of polycarbonate polyol and other polyols, and the other polyols are at least one of polycaprolactone polyol, other polyester polyol, sorbitol and organic silicon polyol. The invention has the advantages of excellent biodegradation performance, high thermal stability and mechanical performance and low energy consumption.
Description
Technical Field
The invention relates to the technical field of PPC (polypropylene random copolymer) resin, and particularly relates to online modified PPC resin and a preparation process thereof.
Background
The development of socio-economic has led to an increasing demand for fossil fuels by humans, resulting in carbon dioxide (CO)2) The discharge amount of (2) is gradually increasingAnd is increased. As is well known, CO2is one of the main gases causing the greenhouse effect, and the global warming brings very serious consequences, such as the subsidence of glaciers, the rise of sea level, desertification and the like, and directly threatens the survival of the human society. Meanwhile, with the continuous improvement of the living standard of human beings, the consumption of plastic products is increased day by day. While the plastic brings convenience to the life of people, a large amount of used plastic waste is increased continuously, a large amount of non-degradable plastic waste causes white pollution, and a non-negligible negative effect is caused to the natural environment which we rely on to live.
When the two problems of greenhouse effect and white pollution are comprehensively inspected, the discovery is that CO2And propylene oxide under the action of a catalyst to generate polymethyl ethylene carbonate (PPC) through copolymerization. PPC can be completely biodegraded, can partially replace the traditional general plastic for use, and is helpful for solving the problem of white pollution caused by the traditional petroleum-based plastic. By using CO2In the synthesis of PPC as a raw material, CO can be used2The greenhouse effect is relieved, and the dependence of plastics on petroleum resources is reduced; on the other hand, a fully biodegradable material can be obtained if the CO discharged by industrial production can be treated2The PPC is prepared into degradable PPC and widely used, which can relieve the greenhouse effect to a certain extent and is beneficial to reducing white pollution.
The PPC serving as a novel aliphatic polyester has good degradation performance and barrier property, and has the advantages of transparency, no toxicity and the like, so that the PPC has a good application prospect in the aspects of food packaging, medical materials, adhesives, engineering plastics and the like. The PPC has asymmetric molecular chain structure and good flexibility, belongs to completely amorphous plastics, has the glass transition temperature of about 35 ℃, small tensile strength (3-30MPa and closely related to the test temperature), extremely high elongation at break (more than 700 percent), strong deformation recovery after stretching and strong temperature sensitivity of the tensile strength. However, the melt processing temperature of PPC is above 100 ℃, thermal degradation occurs near 170 ℃, thermal stability is poor, and the mechanical properties of PPC are relatively poor.
Chinese patent application CN1426430A discloses thermoplastic polyurethane elastomers (TPUs) prepared with polypropylene carbonate soft segments comprising: a) poly (trimethylene carbonate) glycol (PTMC glycol) as a soft segment; b) a diisocyanate; and c) at least one diol which reacts with the diisocyanate to form a hard segment in an amount of 10 to 55% by weight of the composition, wherein the hard segment is defined as the sum of the diisocyanate reacted with the diol and the unreacted diol moieties. The elastomers are somewhat harder than corresponding TPUs based on polyols well known in the art. The PTMC TPUs had good physical and mechanical properties, including a slightly higher modulus of elasticity than the reference TPU. The abrasion resistance and compression set are also very good compared to polyether TPUs, and the softening temperature and the coefficient of thermal expansion are also improved compared to reference TPUs. In addition, by using PTMC polyols, the transparency of TPUs can be increased and even completely transparent materials can be obtained. However, the heat stability and mechanical properties of the polyurethane elastomer prepared from PTMC polyol are still to be further improved.
Chinese patent application CN109694494A discloses a biodegradable thermoplastic polyurethane elastomer foaming bead and a preparation method thereof, belonging to the technical field of polymers. The polyurethane elastomer foaming bead is composed of the following substances in parts by mass: 100-200 parts of bio-based polyol; 20-100 parts of isocyanate; 10-100 parts of a micromolecular alcohol chain extender; 0.1-10 parts of ultraviolet absorbent; 0.1-10 parts of a catalyst; 1-20 parts of a physical foaming agent; wherein the bio-based polyol is a combination of two or more of poly (methyl ethylene carbonate) diol (PPC), polycaprolactone diol (PCL), polylactic acid (PLA) or Polyglycolide (PGA). The prepared foaming bead can be rapidly degraded while ensuring the original foaming multiplying power, strength and density, and can be widely applied to industries such as packaging and the like. Meanwhile, the patent application also provides a preparation method of the compound, which is scientific, reasonable, simple and feasible. But the biodegradability of the expanded beads is to be further improved.
It is also common to add adjuvants to the polyurethane production process to improve the properties and appearance of the article or to improve the process of its preparation, such as stabilizers, flame retardants, mold inhibitors, antioxidants or UV absorbers. However, the auxiliaries are prepared by melting polyurethane and compounding the auxiliaries after the preparation of the polyurethane is finished, so that the energy consumption is high.
Chinese patent CN102391458A discloses a method for preparing aqueous polyurethane, assistant slurry and an aqueous polyurethane finishing agent, wherein the finishing agent is prepared from aqueous polyurethane and assistant slurry according to a proportion. Firstly, preparing a prepolymer with an end group containing an isocyanate group by using a hydrogenated isocyanate monomer, polyester polyol, a chain extender and other materials under the action of a catalyst, adding deionized water to disperse into a waterborne polyurethane system after a salt forming agent reacts with the prepolymer, and finally adding the chain extender at a low temperature to prepare the waterborne polyurethane. Secondly, uniformly mixing components such as a defoaming agent, a slipping agent, a dispersing agent, a pH regulator, a solvent, a hand feeling agent, a coupling agent and the like according to a ratio to prepare the auxiliary agent slurry. And then the waterborne polyurethane finishing agent for the medical PVC (polyvinyl chloride) gloves is prepared by compounding the waterborne polyurethane and the auxiliary agent slurry, so that the performances of smoothness, easiness in wearing, air permeability and the like of the PVC gloves are improved. However, the above patent adopts a mode of firstly preparing polyurethane and then blending the polyurethane and the auxiliary agent, so that the energy consumption is high.
Therefore, it is necessary to develop an on-line modified PPC resin and a process for preparing the same, which can solve the above-mentioned technical problems.
Disclosure of Invention
The invention aims to overcome the defects of the prior art and provide an on-line modified PPC resin with excellent biodegradability, high thermal stability and mechanical property and low energy consumption and a preparation process thereof.
The invention is realized by the following technical scheme:
the on-line modified PPC resin comprises the following raw materials in parts by weight: 100 parts of polyol, 15-60 parts of isocyanate, 2.4-17 parts of micromolecular diol, 0.1-0.2 part of catalyst, 3-10 parts of hydroxyl silane and 1-30 parts of auxiliary agent, wherein the polyol is a mixture of polycarbonate polyol and other polyols, and the other polyols are at least one of polycaprolactone polyol, other polyester polyol, sorbitol and organic silicon polyol.
According to the invention, the hydroxysilane is added into the modified PPC resin raw material, so that the thermal stability of the modified PPC resin is obviously improved, and the adhesion phenomenon is prevented.
Preferably, the molar ratio of the polycarbonate polyol to the other polyol is 12-15: 1.
According to the invention, by limiting the weight parts of the raw materials of the online modified PPC resin and the molar ratio of different alcohols in the polyhydric alcohol, the finally prepared online modified PPC resin not only has flexibility, but also has rigidity, and the mechanical property is obviously improved.
Preferably, the auxiliary agent is at least one of polylactic acid, polybutylene adipate terephthalate, polybutylene succinate, calcium carbonate, talcum powder, starch, cellulose and nucleating agent.
The modified PPC resin obtained by modifying the auxiliary agent can meet the performance requirement of the next product by changing the formula, does not need blending modification, and can be directly used.
Preferably, the polycarbonate polyol is polypropylene carbonate polyol or a mixture of polyethylene carbonate polyol and polypropylene carbonate polyol.
More preferably, the molecular weight of the polypropylene carbonate polyol is 1500-4000 and the functionality is 2.
More preferably, the mass ratio of the polyethylene carbonate polyol to the polypropylene carbonate polyol is 1: 4-6.
Preferably, the other polyester polyol is at least one of polyethylene glycol adipate glycol, 1, 4-butanediol adipate glycol, polyethylene glycol sebacate glycol and polyethylene glycol phthalate glycol.
More preferably, the other polyester polyol is at least one of polyethylene adipate glycol and poly (phthalic acid) glycol.
Preferably, the silicone polyol is an organosiloxane diol.
Preferably, the polyol is one of a combination of polycarbonate polyol and polycaprolactone polyol, polycarbonate polyol and other polyester polyols, polycarbonate polyol and sorbitol, polycarbonate polyol and silicone polyol, polycarbonate polyol, polycaprolactone polyol and other polyester polyols, polycarbonate polyol, other polyester polyols and sorbitol, polycarbonate polyol, other polyester polyols and silicone polyol, polycarbonate polyol, polycaprolactone polyol, other polyester polyols and sorbitol, polycaprolactone polyol, other polyester polyols, sorbitol and silicone polyol.
More preferably, the other polyol is a mixture of other polyester polyol and sorbitol.
more preferably, the mass ratio of the other polyester polyol to sorbitol is 2-3: 1.
Preferably, the isocyanate is at least one of 4,4 '-diphenylmethane diisocyanate, toluene diisocyanate, isophorone diisocyanate, 4' -dicyclohexylmethane diisocyanate, and hexamethylene diisocyanate.
More preferably, the isocyanate is at least one of 4, 4' -diphenylmethane diisocyanate, toluene diisocyanate, and isophorone diisocyanate.
Preferably, the small molecular diol is at least one of ethylene glycol, 1, 4-butanediol, propylene glycol, 1, 4-cyclohexanediol and neopentyl glycol.
More preferably, the small molecule diol is at least one of 1, 4-butanediol, propylene glycol and 1, 4-cyclohexanediol.
More preferably, the small molecule diol is a mixture of 1, 4-butanediol, propylene glycol, 1, 4-cyclohexanediol.
More preferably, the mass ratio of the 1, 4-butanediol to the propylene glycol to the 1, 4-cyclohexanediol is 2-4:1: 0.5-2.
preferably, the catalyst includes at least one of tin-based, bismuth-based, and butyl titanate.
More preferably, the tin includes at least one of stannous octoate, stannous isooctoate, tributyl methoxy tin, t-butoxy tin, phenoxy tin, stannic chloride, stannic bromide, and acetylated tin.
More preferably, the bismuth group includes at least one of bismuth nitrate and bismuth naphthenate.
More preferably, the catalyst is a mixture of tin species and butyl titanate.
More preferably, the mass ratio of the tin species to the butyl titanate is 1: 2-3.
The invention also relates to a preparation method of the online modified PPC resin, which comprises the following steps:
(1) mixing polyol, isocyanate, micromolecular diol, a catalyst and hydroxyl silane to obtain a mixture A;
(2) And injecting the mixture A into a feed inlet of a double-screw extruder, adding the auxiliary agent into the middle section of the extruder, extruding, granulating underwater, and drying to obtain the composite material.
Preferably, the step (1) includes the steps of: simultaneously heating the polyalcohol, the isocyanate, the micromolecular diol, the catalyst and the hydroxyl silane to 50-80 ℃, and mixing to obtain a mixture A.
Preferably, the step (2) includes the steps of: and (2) injecting the mixture A into a feed inlet of a double-screw extruder through a casting machine, wherein the temperature of 360mm multiplied by 15 sections is 130-170 ℃ in 1-7 sections, and the temperature of 8-15 sections is 150-200 ℃, adding an auxiliary agent into 6-8 sections in the middle section of the extruder, reacting for 1.5-3 minutes, extruding, granulating underwater at 30-60 ℃, and drying to obtain the high-performance high-strength. The section 1 is closest to the feed inlet.
The double-screw extruder is a 95-type double-screw extruder, the diameter of a screw is 93.4mm, and the length-diameter ratio is 60: 1.
More preferably, the preparation method of the in-line modified PPC resin comprises the steps of:
(1) Simultaneously heating polyol, isocyanate, micromolecular diol, a catalyst and hydroxyl silane to 50-80 ℃, and mixing to obtain a mixture A;
(2) And (2) injecting the mixture A into a feed inlet of a double-screw extruder through a casting machine, wherein the temperature of 360mm multiplied by 15 sections is 130-170 ℃ in 1-7 sections, and the temperature of 8-15 sections is 150-200 ℃, adding an auxiliary agent into 6-8 sections in the middle section of the extruder, reacting for 1.5-3 minutes, extruding, granulating underwater at 30-60 ℃, and drying to obtain the high-performance high-strength.
The invention has the beneficial effects that:
According to the invention, the hydroxysilane is added into the modified PPC resin raw material, so that the thermal stability, the mechanical property and the biodegradability of the modified PPC resin are obviously improved, and the adhesion phenomenon is prevented.
According to the invention, by limiting the weight parts of the raw materials of the online modified PPC resin and the molar ratio of the mixed polyol of the polycarbonate polyol and other polyols in the polyol, the finally prepared online modified PPC resin not only has flexibility, but also has rigidity, and the mechanical property and the biodegradation property are obviously improved. Particularly, when polycarbonate polyol, other polyester polyol and sorbitol are used together as polyol, the proportion of different polyols is limited, and the mechanical property of the finally prepared online modified PPC resin is obviously improved.
According to the invention, specific polyhydric alcohol, isocyanate, micromolecular diol and catalyst are selected, the component ratio of each component is limited, especially the micromolecular diol is limited to be a mixture of 1, 4-butanediol, propanediol and 1, 4-cyclohexanediol, the molecular weight of the finally prepared PC resin derivative can reach more than 10 ten thousands, the high temperature resistance can reach more than 120 ℃, and the hardening and adhesion phenomena are still avoided at the temperature.
The invention further limits the catalyst to be a mixture of tin and butyl titanate, and the mass ratio of the tin and the butyl titanate has a remarkable influence on the performance of a final product. The synthesis reaction of the modified PPC can be further controlled by controlling the mass ratio of the two catalysts, and the mechanical property, the thermal stability and the biodegradability of the finally prepared product are obviously improved.
the invention adopts a one-step method to prepare the online modified PPC resin, and the preparation process does not need to add a solvent, the preparation is simple, the cost and the energy consumption are lower, the processing performance is excellent, and no harmful gas is discharged in the preparation process.
According to the invention, the auxiliary agent is used for modifying the PPC resin in the process of preparing the PPC resin, the modification is more uniform, the modification and the preparation are completed in one step, the PPC resin does not need to be prepared first and then is melted and compounded with the auxiliary agent, and the energy consumption is lower. The modified PPC resin obtained by modifying the auxiliary agent can meet the performance requirement of the next product by changing the formula, does not need blending modification, and can be directly used.
In the preparation process, the mechanical property and the biodegradation property of the prepared on-line modified PPC resin are obviously improved by limiting the reaction temperature of different charging barrels before and after the preparation, the temperature of 1-7 sections is 130-170 ℃, and the temperature of 8-15 sections is 150-200 ℃.
The film prepared by taking the online modified PPC resin prepared by the invention as a raw material has excellent elongation at break and tear strength, has high barrier property to oxygen and water vapor, can realize complete biodegradation by composting, has special properties such as good compatibility with other biodegradable materials, and can be widely applied to industries such as packaging, mulching films, disposable articles and the like.
Detailed Description
The invention will be further described with reference to specific embodiments, and the advantages and features of the invention will become apparent as the description proceeds. These examples are illustrative only and do not limit the scope of the present invention in any way. It will be understood by those skilled in the art that various changes in form and details may be made therein without departing from the spirit and scope of the invention, and that such changes and modifications may be made without departing from the spirit and scope of the invention.
The twin-screw extruder of the present invention is a 95 type twin-screw extruder, unless otherwise specified, and has a screw diameter of 93.4mm and a length-to-diameter ratio of 60: 1.
Example 1
The on-line modified PPC resin comprises the following raw materials in parts by weight: 100 parts of polyol, 15 parts of 4, 4' -diphenylmethane diisocyanate, 2.4 parts of 1, 4-butanediol, 0.1 part of catalyst, 3 parts of hydroxysilane and 1 part of polylactic acid, wherein the polyol is a mixture of polypropylene carbonate diol (with the molecular weight of 1500) and polycaprolactone diol (with the molar ratio of 12: 1).
the catalyst is a mixture of stannous octoate and butyl titanate, and the mass ratio of the stannous octoate to the butyl titanate is 1: 2.
The preparation method of the online modified PPC resin comprises the following steps:
(1) Simultaneously heating polyol, 4' -diphenylmethane diisocyanate, 1, 4-butanediol, a catalyst and hydroxysilane to 50 ℃, and mixing to obtain a mixture A;
(2) And (3) injecting the mixture A into a feed inlet of a double-screw extruder through a casting machine, wherein the temperature of 360mm multiplied by 15 sections is 130 ℃ in 1-7 sections, and the temperature of 8-15 sections is 150 ℃, adding polylactic acid into the section 6 in the middle section of the extruder, reacting for 1.5 minutes, extruding, granulating underwater at 30 ℃, and drying to obtain the polylactic acid.
example 2
an on-line modified PPC resin is different from the resin in the embodiment 2 only in that polycaprolactone diol is replaced by a mixture of polyethylene glycol adipate diol and sorbitol, the mass ratio of the polycaprolactone diol to the polyethylene glycol adipate diol is 2:1, and the other conditions are the same.
Example 3
The on-line modified PPC resin comprises the following raw materials in parts by weight: 100 parts of polyol, 60 parts of toluene diisocyanate, 17 parts of propylene glycol, 0.2 part of catalyst, 10 parts of hydroxyl silane and 15 parts of polybutylene adipate terephthalate, wherein the polyol is a mixture of polycarbonate polyol and other polyol (the molar ratio is 15: 1).
The polycarbonate polyol is a mixture of polyethylene carbonate dihydric alcohol (with a molecular weight of 4000) and polypropylene carbonate dihydric alcohol (with a molecular weight of 4000) (with a mass ratio of 1: 6); the other polyhydric alcohols are a mixture of poly (phthalic acid) glycol ester diol and sorbitol (the mass ratio is 3: 1); the catalyst is a mixture of tributyl methoxy tin and butyl titanate, and the mass ratio of the tributyl methoxy tin to the butyl titanate is 1: 3.
The preparation method of the online modified PPC resin comprises the following steps:
(1) Simultaneously heating polyol, toluene diisocyanate, propylene glycol, a catalyst and hydroxyl silane to 80 ℃, and mixing to obtain a mixture A;
(2) And (2) injecting the mixture A into a feed inlet of a double-screw extruder through a casting machine, wherein the temperature of 360mm multiplied by 15 sections is 170 ℃ in 1-7 sections, and the temperature of 8-15 sections is 200 ℃, adding polybutylene adipate-terephthalate into the section 8 in the middle section of the extruder, reacting for 3 minutes, extruding, granulating under water at 60 ℃, and drying to obtain the polybutylene adipate-terephthalate.
Example 4
The on-line modified PPC resin comprises the following raw materials in parts by weight: 100 parts of polyol, 35 parts of isophorone diisocyanate, 10 parts of 1, 4-cyclohexanediol, 0.15 part of catalyst, 3-10 parts of hydroxyl silane and 1-30 parts of talcum powder, wherein the polyol is a mixture of polycarbonate polyol and other polyol (the molar ratio is 14: 1).
The polycarbonate polyol is a mixture of polyethylene carbonate polyol (with a molecular weight of 2500) and polypropylene carbonate polyol (with a molecular weight of 2500) (with a mass ratio of 1: 4); the other polyhydric alcohol is a mixture of poly (phthalic acid) glycol ester diol and sorbitol (the mass ratio is 2.5: 1); the catalyst is a mixture of tin chloride and butyl titanate, and the mass ratio of the tin chloride to the butyl titanate is 1: 2.
The preparation method of the online modified PPC resin comprises the following steps:
(1) Simultaneously heating polyol, isophorone diisocyanate, 1, 4-cyclohexanediol, a catalyst and hydroxysilane to 65 ℃, and mixing to obtain a mixture A;
(2) and (3) injecting the mixture A into a feed inlet of a double-screw extruder through a casting machine, wherein the temperature of 360mm multiplied by 15 sections is 150 ℃ in 1-7 sections, and the temperature of 8-15 sections is 175 ℃, adding talcum powder into the 7 th section of the middle section of the extruder, reacting for 2 minutes, extruding, granulating under water at 45 ℃, and drying to obtain the compound.
Comparative example 1
the only difference from example 4 is that the molar ratio of polycarbonate polyol to other polyols is 7:1, and the other conditions are the same.
Comparative example 2
The only difference from example 4 is that the other polyol is a mixture of poly (phthalic acid) glycol ester diol and sorbitol in a mass ratio of 4:1, and the rest conditions are the same.
comparative example 3
The catalyst is different from the catalyst in example 4 only in that the catalyst is a mixture of tin chloride and butyl titanate with the mass ratio of 1:1, and the rest conditions are the same.
comparative example 4
The difference from example 4 is only that the temperature of the twin-screw extruder at sections 1-15 is 175 ℃ during the preparation of the in-line modified PPC resin, and the rest conditions are the same.
Comparative example 5
The difference from example 4 is only that no hydroxysilane is added, and the other conditions are the same, and the specific preparation process is as follows:
(1) Simultaneously heating polyol, isophorone diisocyanate, 1, 4-cyclohexanediol and a catalyst to 65 ℃, and mixing to obtain a mixture A;
(2) And (3) injecting the mixture A into a feed inlet of a double-screw extruder through a casting machine, wherein the temperature of 360mm multiplied by 15 sections is 150 ℃ in 1-7 sections, and the temperature of 8-15 sections is 175 ℃, adding talcum powder into the 7 th section of the middle section of the extruder, reacting for 2 minutes, extruding, granulating under water at 45 ℃, and drying to obtain the compound.
Test example 1
The mechanical property test of the online modified PPC resin of the examples 1-4 and the comparative examples 1-5 refers to GB/T31124-2014, and the sample is 1A type in GB/T1040.2-2006.
The results are shown in Table 1.
TABLE 1 on-line modified PPC resin mechanical Properties test
Tensile strength/MPa | |
example 1 | 33 |
Example 2 | 37 |
example 3 | 39 |
Example 4 | 40 |
Comparative example 1 | 32 |
Comparative example 2 | 30 |
Comparative example 3 | 28 |
Comparative example 4 | 29 |
Comparative example 5 | 23 |
Test example 2
The in-line modified PPC resins of example 1, example 4 and comparative examples 1, 3-5 were subjected to biodegradation tests, see GB/T19277-2003. The higher the percentage of biodegradation after 45 days, the better the degree of degradation. The results are shown in Table 2.
TABLE 2 on-line modified PPC resin biodegradability test
The technical means disclosed by the scheme of the invention are not limited to the technical means disclosed by the technical means, and the technical scheme also comprises the technical scheme formed by any combination of the technical characteristics. While the foregoing is directed to embodiments of the present invention, it will be appreciated by those skilled in the art that various changes may be made in the embodiments without departing from the principles of the invention, and that such changes and modifications are intended to be included within the scope of the invention.
Claims (10)
1. The on-line modified PPC resin comprises the following raw materials in parts by weight: 100 parts of polyol, 15-60 parts of isocyanate, 2.4-17 parts of micromolecular diol, 0.1-0.2 part of catalyst, 3-10 parts of hydroxyl silane and 1-30 parts of auxiliary agent, wherein the polyol is a mixture of polycarbonate polyol and other polyols, and the other polyols are at least one of polycaprolactone polyol, other polyester polyol, sorbitol and organic silicon polyol.
2. The on-line modified PPC resin of claim 1, wherein the auxiliary agent is at least one of polylactic acid, polybutylene adipate terephthalate, polybutylene succinate, calcium carbonate, talc, starch, cellulose, and nucleating agent.
3. The on-line modified PPC resin of claim 1, wherein said polycarbonate polyol and other polyols are present in a molar ratio of 12-15: 1.
4. The on-line modified PPC resin of claim 1, wherein said polycarbonate polyol is a polypropylene carbonate polyol or a mixture of a polyethylene carbonate polyol and a polypropylene carbonate polyol, said polypropylene carbonate polyol preferably having a molecular weight of 1500-4000 and a functionality of 2; the other polyester polyol is at least one of polyethylene glycol adipate glycol, 1, 4-butanediol adipate glycol, polysebacate glycol ester glycol and poly-phthalic acid glycol ester glycol; the silicone polyol is an organosiloxane diol.
5. The on-line modified PPC resin of claim 1, wherein said polyol is one of a combination of polycarbonate polyol and polycaprolactone polyol, polycarbonate polyol and other polyester polyols, polycarbonate polyol and sorbitol, polycarbonate polyol and silicone polyol, polycarbonate polyol, polycaprolactone polyol and other polyester polyols, polycarbonate polyol, other polyester polyols and sorbitol, polycarbonate polyol, other polyester polyols and silicone polyol, polycarbonate polyol, polycaprolactone polyol, other polyester polyols and sorbitol, polycarbonate polyol, polycaprolactone polyol, other polyester polyols, sorbitol and silicone polyol.
6. The on-line modified PPC resin according to claim 1, wherein said isocyanate is at least one of 4,4 '-diphenylmethane diisocyanate, toluene diisocyanate, isophorone diisocyanate, 4' -dicyclohexylmethane diisocyanate, and hexamethylene diisocyanate; the micromolecular diol is at least one of ethylene glycol, 1, 4-butanediol, propylene glycol, 1, 4-cyclohexanediol and neopentyl glycol; the catalyst comprises at least one of tin, bismuth and butyl titanate.
7. The on-line modified PPC resin of claim 1, wherein the catalyst is a mixture of tin and butyl titanate in a mass ratio of 1: 2-3.
8. A process for the preparation of the in-line modified PPC resin of any of claims 1-7, comprising the steps of:
(1) Mixing polyol, isocyanate, micromolecular diol, a catalyst and hydroxyl silane to obtain a mixture A;
(2) And injecting the mixture A into a feed inlet of a double-screw extruder, adding the auxiliary agent into the middle section of the extruder, extruding, granulating underwater, and drying to obtain the composite material.
9. the method according to claim 8, wherein the step (1) comprises the steps of: simultaneously heating the polyalcohol, the isocyanate, the micromolecular diol, the catalyst and the hydroxyl silane to 50-80 ℃, and mixing to obtain a mixture A.
10. The method of claim 8, wherein the step (2) comprises the steps of: and (2) injecting the mixture A into a feed inlet of a double-screw extruder through a casting machine, wherein the temperature of 360mm multiplied by 15 sections is 130-170 ℃ in 1-7 sections, and the temperature of 8-15 sections is 150-200 ℃, adding an auxiliary agent into 6-8 sections in the middle section of the extruder, reacting for 1.5-3 minutes, extruding, granulating underwater at 30-60 ℃, and drying to obtain the high-performance high-strength.
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CN201911019341.2A CN110563917B (en) | 2019-10-24 | 2019-10-24 | Online modified PPC resin and preparation process thereof |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CN201911019341.2A CN110563917B (en) | 2019-10-24 | 2019-10-24 | Online modified PPC resin and preparation process thereof |
Publications (2)
Publication Number | Publication Date |
---|---|
CN110563917A true CN110563917A (en) | 2019-12-13 |
CN110563917B CN110563917B (en) | 2020-09-04 |
Family
ID=68785910
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
CN201911019341.2A Active CN110563917B (en) | 2019-10-24 | 2019-10-24 | Online modified PPC resin and preparation process thereof |
Country Status (1)
Country | Link |
---|---|
CN (1) | CN110563917B (en) |
Cited By (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN114891183A (en) * | 2022-06-09 | 2022-08-12 | 江西省科学院应用化学研究所 | Waterborne polyurethane modified starch dispersion liquid and preparation method thereof |
WO2024062300A1 (en) * | 2022-09-20 | 2024-03-28 | SDIP Innovations Pty Ltd | Biodegradable elastomeric copolymer |
Citations (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN104072952A (en) * | 2014-06-17 | 2014-10-01 | 浙江杭州鑫富药业股份有限公司 | Full-biodegradable mulching film with excellent transverse and longitudinal tearing property |
CN107298845A (en) * | 2017-06-13 | 2017-10-27 | 上海恒安聚氨酯股份有限公司 | Oil resistant weather-proof polyurethane thermoplastic elastomer (TPE) and preparation method thereof |
CN107652664A (en) * | 2017-09-28 | 2018-02-02 | 东莞市雄林新材料科技股份有限公司 | A kind of photosensitive colour-changing TPU film for adhering film to glass and preparation method thereof |
CN109694494A (en) * | 2018-12-21 | 2019-04-30 | 山东一诺威聚氨酯股份有限公司 | Biodegradable thermoplastic polyurethane elastomer expanded bead and preparation method thereof |
-
2019
- 2019-10-24 CN CN201911019341.2A patent/CN110563917B/en active Active
Patent Citations (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN104072952A (en) * | 2014-06-17 | 2014-10-01 | 浙江杭州鑫富药业股份有限公司 | Full-biodegradable mulching film with excellent transverse and longitudinal tearing property |
CN107298845A (en) * | 2017-06-13 | 2017-10-27 | 上海恒安聚氨酯股份有限公司 | Oil resistant weather-proof polyurethane thermoplastic elastomer (TPE) and preparation method thereof |
CN107652664A (en) * | 2017-09-28 | 2018-02-02 | 东莞市雄林新材料科技股份有限公司 | A kind of photosensitive colour-changing TPU film for adhering film to glass and preparation method thereof |
CN109694494A (en) * | 2018-12-21 | 2019-04-30 | 山东一诺威聚氨酯股份有限公司 | Biodegradable thermoplastic polyurethane elastomer expanded bead and preparation method thereof |
Non-Patent Citations (2)
Title |
---|
傅敏等: "高性能透明聚氨酯树脂的合成研究", 《聚氨酯工业》 * |
郭云飞等: "有机硅改性聚氨酯的合成及其性能", 《纺织学报》 * |
Cited By (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN114891183A (en) * | 2022-06-09 | 2022-08-12 | 江西省科学院应用化学研究所 | Waterborne polyurethane modified starch dispersion liquid and preparation method thereof |
CN114891183B (en) * | 2022-06-09 | 2024-01-26 | 江西省科学院应用化学研究所 | Aqueous polyurethane modified starch dispersion liquid and preparation method thereof |
WO2024062300A1 (en) * | 2022-09-20 | 2024-03-28 | SDIP Innovations Pty Ltd | Biodegradable elastomeric copolymer |
Also Published As
Publication number | Publication date |
---|---|
CN110563917B (en) | 2020-09-04 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
EP2129700B1 (en) | Low haze thermoplastic polyurethane using mixture of chain extenders including 1,3-and 1,4-cyclohexanedimethanol | |
US20100109200A1 (en) | Thermoplastic Polyurethane Prepared Using A Mixture Of Polyester Diol And Poly(Propylene Oxide) Diol | |
CN101679597A (en) | polyurethane polymer | |
CN110894278B (en) | High-transparency thermoplastic polyurethane elastomer for film blowing and preparation method thereof | |
CN110563917B (en) | Online modified PPC resin and preparation process thereof | |
CN101899139A (en) | Method for preparing polylactic acid-based high-elasticity copolymer | |
KR20130135758A (en) | Polylactic acid resin and film for packaging comprising the same | |
JP2023123869A (en) | Thermoplastic polyurethane resin elastomer | |
CN113248680A (en) | High-transparency high-yellowing-resistance thermoplastic polyurethane for electronics and preparation method thereof | |
TW202012483A (en) | Thermoplastic polyurethane, foamed thermoplastic polyurethane elastomer particles comprising the same, and methods for producing such | |
CN113968954B (en) | Degradable thermoplastic polyurethane elastomer and preparation method and application thereof | |
Liu et al. | Cross-linked poly (ester urethane)/starch composite films with high starch content as sustainable food-packaging materials: Influence of cross-link density | |
CN110563916B (en) | PPC resin derivative and online preparation method thereof | |
US12065537B2 (en) | Shape memory polymer based on poly(hydroxyalkanoates) | |
JP5304228B2 (en) | Method for producing three-dimensional crosslinked polyurethane, and molded body using the same | |
CN113512275A (en) | High-melt-strength compostable degradable material and preparation method thereof | |
KR20160092865A (en) | Biodegradable film composition consisting of Polylactic acid | |
CN111499826B (en) | Thermoplastic polyurethane elastomer and preparation method thereof | |
CN113956429A (en) | Thermoplastic polyurethane elastomer and preparation method thereof | |
CN113896955A (en) | Starch-based sheet composition and preparation method thereof | |
CN113943478A (en) | Flexible transparent degradable packaging film | |
TW202122441A (en) | Thermoplastic polyurethane, method for producing the same, and molded article | |
JP2853118B2 (en) | Method for producing thermoplastic polyurethane elastomer | |
JP2752881B2 (en) | Polyester tape | |
JP2747195B2 (en) | Polyester biaxially stretched hollow molded body |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
PB01 | Publication | ||
PB01 | Publication | ||
SE01 | Entry into force of request for substantive examination | ||
SE01 | Entry into force of request for substantive examination | ||
GR01 | Patent grant | ||
GR01 | Patent grant | ||
TR01 | Transfer of patent right | ||
TR01 | Transfer of patent right |
Effective date of registration: 20231106 Address after: Building 605, No. 10, No. 78 Keling Road, Science and Technology City, Suzhou High tech Zone, Suzhou City, Jiangsu Province, 215000 Patentee after: Suzhou Kunsheng Biodegradable New Materials Co.,Ltd. Address before: 225400 Xiqiao Industrial Park, Huangqiao Town, Taixing City, Taizhou City, Jiangsu Province Patentee before: JIANGSU ZHONGKE JINLONG ENVIRONMENTAL PROTECTIVE NEW MATERIALS Co.,Ltd. |