CN111253341A - 一种环氧腰果酚低聚酯型增塑剂及其制备与应用 - Google Patents
一种环氧腰果酚低聚酯型增塑剂及其制备与应用 Download PDFInfo
- Publication number
- CN111253341A CN111253341A CN202010091020.XA CN202010091020A CN111253341A CN 111253341 A CN111253341 A CN 111253341A CN 202010091020 A CN202010091020 A CN 202010091020A CN 111253341 A CN111253341 A CN 111253341A
- Authority
- CN
- China
- Prior art keywords
- cardanol
- oligoester
- epoxy
- plasticizer
- reaction
- 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
- JOLVYUIAMRUBRK-UTOQUPLUSA-N Cardanol Chemical compound OC1=CC=CC(CCCCCCC\C=C/C\C=C/CC=C)=C1 JOLVYUIAMRUBRK-UTOQUPLUSA-N 0.000 title claims abstract description 107
- JOLVYUIAMRUBRK-UHFFFAOYSA-N 11',12',14',15'-Tetradehydro(Z,Z-)-3-(8-Pentadecenyl)phenol Natural products OC1=CC=CC(CCCCCCCC=CCC=CCC=C)=C1 JOLVYUIAMRUBRK-UHFFFAOYSA-N 0.000 title claims abstract description 104
- YLKVIMNNMLKUGJ-UHFFFAOYSA-N 3-Delta8-pentadecenylphenol Natural products CCCCCCC=CCCCCCCCC1=CC=CC(O)=C1 YLKVIMNNMLKUGJ-UHFFFAOYSA-N 0.000 title claims abstract description 104
- FAYVLNWNMNHXGA-UHFFFAOYSA-N Cardanoldiene Natural products CCCC=CCC=CCCCCCCCC1=CC=CC(O)=C1 FAYVLNWNMNHXGA-UHFFFAOYSA-N 0.000 title claims abstract description 104
- PTFIPECGHSYQNR-UHFFFAOYSA-N cardanol Natural products CCCCCCCCCCCCCCCC1=CC=CC(O)=C1 PTFIPECGHSYQNR-UHFFFAOYSA-N 0.000 title claims abstract description 104
- 229920002601 oligoester Polymers 0.000 title claims abstract description 74
- 239000004014 plasticizer Substances 0.000 title claims abstract description 64
- 239000004593 Epoxy Substances 0.000 title claims abstract description 46
- 238000002360 preparation method Methods 0.000 title claims abstract description 15
- 238000006243 chemical reaction Methods 0.000 claims abstract description 41
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims abstract description 26
- WFDIJRYMOXRFFG-UHFFFAOYSA-N Acetic anhydride Chemical compound CC(=O)OC(C)=O WFDIJRYMOXRFFG-UHFFFAOYSA-N 0.000 claims abstract description 21
- 239000002904 solvent Substances 0.000 claims abstract description 21
- 239000003054 catalyst Substances 0.000 claims abstract description 18
- 229960000583 acetic acid Drugs 0.000 claims abstract description 13
- 239000012362 glacial acetic acid Substances 0.000 claims abstract description 13
- 150000002596 lactones Chemical class 0.000 claims abstract description 11
- 150000002736 metal compounds Chemical class 0.000 claims abstract description 10
- 150000004965 peroxy acids Chemical class 0.000 claims abstract description 8
- 239000000047 product Substances 0.000 claims description 45
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 30
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 24
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 claims description 24
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical group ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims description 21
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 21
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 14
- 239000000706 filtrate Substances 0.000 claims description 14
- 238000001914 filtration Methods 0.000 claims description 14
- 238000000034 method Methods 0.000 claims description 14
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 claims description 14
- 239000012074 organic phase Substances 0.000 claims description 14
- 238000001035 drying Methods 0.000 claims description 13
- 238000005406 washing Methods 0.000 claims description 11
- 239000012043 crude product Substances 0.000 claims description 9
- 238000010992 reflux Methods 0.000 claims description 9
- PAPBSGBWRJIAAV-UHFFFAOYSA-N ε-Caprolactone Chemical compound O=C1CCCCCO1 PAPBSGBWRJIAAV-UHFFFAOYSA-N 0.000 claims description 9
- NHQDETIJWKXCTC-UHFFFAOYSA-N 3-chloroperbenzoic acid Chemical compound OOC(=O)C1=CC=CC(Cl)=C1 NHQDETIJWKXCTC-UHFFFAOYSA-N 0.000 claims description 7
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 claims description 7
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical class [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 claims description 7
- 239000012153 distilled water Substances 0.000 claims description 7
- 230000007935 neutral effect Effects 0.000 claims description 7
- 229910052757 nitrogen Inorganic materials 0.000 claims description 7
- 239000012071 phase Substances 0.000 claims description 7
- 238000002390 rotary evaporation Methods 0.000 claims description 7
- GEHJYWRUCIMESM-UHFFFAOYSA-L sodium sulfite Chemical class [Na+].[Na+].[O-]S([O-])=O GEHJYWRUCIMESM-UHFFFAOYSA-L 0.000 claims description 7
- 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 claims description 7
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 claims description 6
- YEJRWHAVMIAJKC-UHFFFAOYSA-N 4-Butyrolactone Chemical compound O=C1CCCO1 YEJRWHAVMIAJKC-UHFFFAOYSA-N 0.000 claims description 4
- OZJPLYNZGCXSJM-UHFFFAOYSA-N 5-valerolactone Chemical compound O=C1CCCCO1 OZJPLYNZGCXSJM-UHFFFAOYSA-N 0.000 claims description 4
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims description 4
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 claims description 4
- JVTAAEKCZFNVCJ-UHFFFAOYSA-N lactic acid Chemical compound CC(O)C(O)=O JVTAAEKCZFNVCJ-UHFFFAOYSA-N 0.000 claims description 4
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 claims description 4
- 239000003960 organic solvent Substances 0.000 claims description 4
- VLTRZXGMWDSKGL-UHFFFAOYSA-N perchloric acid Chemical compound OCl(=O)(=O)=O VLTRZXGMWDSKGL-UHFFFAOYSA-N 0.000 claims description 4
- 230000035484 reaction time Effects 0.000 claims description 4
- CIHOLLKRGTVIJN-UHFFFAOYSA-N tert‐butyl hydroperoxide Chemical compound CC(C)(C)OO CIHOLLKRGTVIJN-UHFFFAOYSA-N 0.000 claims description 4
- JIAARYAFYJHUJI-UHFFFAOYSA-L zinc dichloride Chemical compound [Cl-].[Cl-].[Zn+2] JIAARYAFYJHUJI-UHFFFAOYSA-L 0.000 claims description 4
- 150000008064 anhydrides Chemical class 0.000 claims description 3
- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical compound COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-UHFFFAOYSA-N 0.000 claims description 2
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 claims description 2
- 125000005234 alkyl aluminium group Chemical group 0.000 claims description 2
- PNOXNTGLSKTMQO-UHFFFAOYSA-L diacetyloxytin Chemical compound CC(=O)O[Sn]OC(C)=O PNOXNTGLSKTMQO-UHFFFAOYSA-L 0.000 claims description 2
- 235000019253 formic acid Nutrition 0.000 claims description 2
- 239000004310 lactic acid Substances 0.000 claims description 2
- 235000014655 lactic acid Nutrition 0.000 claims description 2
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 claims description 2
- 235000005074 zinc chloride Nutrition 0.000 claims description 2
- 239000011592 zinc chloride Substances 0.000 claims description 2
- 239000004800 polyvinyl chloride Substances 0.000 abstract description 41
- 229920000915 polyvinyl chloride Polymers 0.000 abstract description 41
- 230000015556 catabolic process Effects 0.000 abstract description 6
- 238000006731 degradation reaction Methods 0.000 abstract description 6
- 230000000694 effects Effects 0.000 abstract description 6
- 229920000728 polyester Polymers 0.000 abstract description 6
- 239000002994 raw material Substances 0.000 abstract description 6
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 abstract description 5
- IXCSERBJSXMMFS-UHFFFAOYSA-N hydrogen chloride Substances Cl.Cl IXCSERBJSXMMFS-UHFFFAOYSA-N 0.000 abstract description 5
- 229910000041 hydrogen chloride Inorganic materials 0.000 abstract description 5
- 238000001228 spectrum Methods 0.000 description 9
- 150000002148 esters Chemical class 0.000 description 7
- 239000000203 mixture Substances 0.000 description 6
- 238000009472 formulation Methods 0.000 description 5
- 229920003023 plastic Polymers 0.000 description 5
- 239000004033 plastic Substances 0.000 description 5
- 239000007787 solid Substances 0.000 description 5
- 244000226021 Anacardium occidentale Species 0.000 description 4
- 229910052799 carbon Inorganic materials 0.000 description 4
- 235000020226 cashew nut Nutrition 0.000 description 4
- OEIWPNWSDYFMIL-UHFFFAOYSA-N dioctyl benzene-1,4-dicarboxylate Chemical compound CCCCCCCCOC(=O)C1=CC=C(C(=O)OCCCCCCCC)C=C1 OEIWPNWSDYFMIL-UHFFFAOYSA-N 0.000 description 4
- 229910052739 hydrogen Inorganic materials 0.000 description 4
- 239000001257 hydrogen Substances 0.000 description 4
- 239000000463 material Substances 0.000 description 4
- 239000008029 phthalate plasticizer Substances 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- 238000012360 testing method Methods 0.000 description 4
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 3
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 3
- 230000036541 health Effects 0.000 description 3
- 238000012986 modification Methods 0.000 description 3
- 230000004048 modification Effects 0.000 description 3
- 239000010466 nut oil Substances 0.000 description 3
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N phenol group Chemical group C1(=CC=CC=C1)O ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 3
- 229920000642 polymer Polymers 0.000 description 3
- 238000012545 processing Methods 0.000 description 3
- 238000003756 stirring Methods 0.000 description 3
- 238000005979 thermal decomposition reaction Methods 0.000 description 3
- 238000001757 thermogravimetry curve Methods 0.000 description 3
- 239000004721 Polyphenylene oxide Substances 0.000 description 2
- 125000000217 alkyl group Chemical group 0.000 description 2
- 239000006227 byproduct Substances 0.000 description 2
- 125000001309 chloro group Chemical group Cl* 0.000 description 2
- 238000000354 decomposition reaction Methods 0.000 description 2
- 238000005034 decoration Methods 0.000 description 2
- HBGGXOJOCNVPFY-UHFFFAOYSA-N diisononyl phthalate Chemical compound CC(C)CCCCCCOC(=O)C1=CC=CC=C1C(=O)OCCCCCCC(C)C HBGGXOJOCNVPFY-UHFFFAOYSA-N 0.000 description 2
- 238000006735 epoxidation reaction Methods 0.000 description 2
- 125000003700 epoxy group Chemical group 0.000 description 2
- 230000009477 glass transition Effects 0.000 description 2
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 2
- 231100000053 low toxicity Toxicity 0.000 description 2
- 229920000570 polyether Polymers 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- 239000010909 process residue Substances 0.000 description 2
- 229920006395 saturated elastomer Polymers 0.000 description 2
- 239000002699 waste material Substances 0.000 description 2
- CSDQQAQKBAQLLE-UHFFFAOYSA-N 4-(4-chlorophenyl)-4,5,6,7-tetrahydrothieno[3,2-c]pyridine Chemical compound C1=CC(Cl)=CC=C1C1C(C=CS2)=C2CCN1 CSDQQAQKBAQLLE-UHFFFAOYSA-N 0.000 description 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- 238000000944 Soxhlet extraction Methods 0.000 description 1
- 238000005411 Van der Waals force Methods 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 150000001491 aromatic compounds Chemical group 0.000 description 1
- 239000004566 building material Substances 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 238000004040 coloring Methods 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 230000000382 dechlorinating effect Effects 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000007865 diluting Methods 0.000 description 1
- 229920001971 elastomer Polymers 0.000 description 1
- 230000002708 enhancing effect Effects 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- 239000000835 fiber Substances 0.000 description 1
- 235000013305 food Nutrition 0.000 description 1
- 239000012760 heat stabilizer Substances 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 1
- 238000011065 in-situ storage Methods 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 125000001570 methylene group Chemical group [H]C([H])([*:1])[*:2] 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 239000012299 nitrogen atmosphere Substances 0.000 description 1
- 239000003921 oil Substances 0.000 description 1
- 235000019198 oils Nutrition 0.000 description 1
- 239000012785 packaging film Substances 0.000 description 1
- 229920006280 packaging film Polymers 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
- 238000006068 polycondensation reaction Methods 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 238000003825 pressing Methods 0.000 description 1
- 238000000197 pyrolysis Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000012827 research and development Methods 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 238000007151 ring opening polymerisation reaction Methods 0.000 description 1
- 239000003566 sealing material Substances 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 239000004094 surface-active agent Substances 0.000 description 1
- 238000002411 thermogravimetry Methods 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- 230000009466 transformation Effects 0.000 description 1
Images
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D301/00—Preparation of oxiranes
- C07D301/02—Synthesis of the oxirane ring
- C07D301/03—Synthesis of the oxirane ring by oxidation of unsaturated compounds, or of mixtures of unsaturated and saturated compounds
- C07D301/14—Synthesis of the oxirane ring by oxidation of unsaturated compounds, or of mixtures of unsaturated and saturated compounds with organic peracids, or salts, anhydrides or esters thereof
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C67/00—Preparation of carboxylic acid esters
- C07C67/03—Preparation of carboxylic acid esters by reacting an ester group with a hydroxy group
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C67/00—Preparation of carboxylic acid esters
- C07C67/30—Preparation of carboxylic acid esters by modifying the acid moiety of the ester, such modification not being an introduction of an ester group
- C07C67/31—Preparation of carboxylic acid esters by modifying the acid moiety of the ester, such modification not being an introduction of an ester group by introduction of functional groups containing oxygen only in singly bound form
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C69/00—Esters of carboxylic acids; Esters of carbonic or haloformic acids
- C07C69/66—Esters of carboxylic acids having esterified carboxylic groups bound to acyclic carbon atoms and having any of the groups OH, O—metal, —CHO, keto, ether, acyloxy, groups, groups, or in the acid moiety
- C07C69/73—Esters of carboxylic acids having esterified carboxylic groups bound to acyclic carbon atoms and having any of the groups OH, O—metal, —CHO, keto, ether, acyloxy, groups, groups, or in the acid moiety of unsaturated acids
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D303/00—Compounds containing three-membered rings having one oxygen atom as the only ring hetero atom
- C07D303/02—Compounds containing oxirane rings
- C07D303/12—Compounds containing oxirane rings with hydrocarbon radicals, substituted by singly or doubly bound oxygen atoms
- C07D303/16—Compounds containing oxirane rings with hydrocarbon radicals, substituted by singly or doubly bound oxygen atoms by esterified hydroxyl radicals
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/04—Oxygen-containing compounds
- C08K5/10—Esters; Ether-esters
- C08K5/101—Esters; Ether-esters of monocarboxylic acids
- C08K5/105—Esters; Ether-esters of monocarboxylic acids with phenols
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/04—Oxygen-containing compounds
- C08K5/15—Heterocyclic compounds having oxygen in the ring
- C08K5/151—Heterocyclic compounds having oxygen in the ring having one oxygen atom in the ring
- C08K5/1515—Three-membered rings
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L27/00—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Compositions of derivatives of such polymers
- C08L27/02—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Compositions of derivatives of such polymers not modified by chemical after-treatment
- C08L27/04—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Compositions of derivatives of such polymers not modified by chemical after-treatment containing chlorine atoms
- C08L27/06—Homopolymers or copolymers of vinyl chloride
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2201/00—Properties
- C08L2201/08—Stabilised against heat, light or radiation or oxydation
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
Abstract
本发明公开一种环氧腰果酚低聚酯型增塑剂及其制备与应用,其制备方法为(1)将腰果酚、金属化合物催化剂和内酯溶于第一溶剂中反应,得到腰果酚低聚酯;(2)将腰果酚低聚酯与催化剂、冰醋酸和酸酐反应,得到封端的腰果酚低聚酯;(3)将封端的腰果酚低聚酯和过氧酸溶于第二溶剂中反应,得到环氧腰果酚低聚酯型增塑剂。有益效果:本发明以腰果酚为原料制备出安全环保的生物增塑剂,其包含了环氧型增塑剂和聚酯型增塑剂的优点,让PVC制品既有突出的抗低温冲击和非常高的抗撕裂强度能力,又可以续收聚氯乙烯中因光和热降解出来的氯化氢,阻止PVC的连续降解,起到延长PVC制品使用寿命的作用。
Description
技术领域
本发明属于化工领域,涉及一种环氧腰果酚低聚酯型增塑剂及其制备与应用。
背景技术
聚氯乙烯是世界第二大应用树脂,其产品已广泛应用于建筑材料、工业制品、日用品、地板砖、电线电缆、密封材料、纤维、包装膜、发泡材料等。但聚氯乙烯的玻璃化转变温度过高,直接使用无法满足日常条件,因此工业上常采用加入合适增塑剂以将其玻璃化转变温度降低到使用温度以下。增塑剂是指可以提高聚合物塑性的物质,在聚氯乙烯生产中的用量能占到全部添加剂用量的98%。邻苯二甲酸酯类增塑剂是目前应用最广泛的增塑剂,有着色泽浅、电性能好、气味小、增塑效率高、综合性能优异等优点。但研究发现,由于在塑料中,邻苯二甲酸酯类增塑剂与塑化材料分子间由氢键或范德华力连接,两者间没有严格的化学结合键,因此在使用过程中,邻苯二甲酸酯容易从塑料中迁移到外界,造成环境污染,危害人体健康。目前,新型环保增塑剂的研发已成为热点。
聚酯型增塑剂是目前新型增塑剂研发重点之一,其是由饱和二元醇与饱和二元酸通过缩聚反应制备而得的线性高分子聚合物。虽然与低分子量增塑剂相比,一般聚酯的塑化效率较差,粘度较大,加工性和低温性不好,但它具有迁移性小、耐高温、挥发性低、不容易被水和溶剂抽出等特点,是性能很好的耐热性和耐久性增塑剂,在PVC制品中有突出的抗低温冲击和非常高的抗撕裂强度能力。
腰果酚是腰果壳油的主要成分,也是腰果油的副产物,易于提取、价格低廉、可再生,与大多数橡胶都有很好的相容性。腰果酚结构为苯酚间位一条含有0~3个双键的15碳烷基链,其酚羟基和烷基链都有极大的改造潜力。目前,腰果酚的衍生物已被广泛应用于表面活性剂、胶黏剂、涂料、高分子助剂、增塑剂、摩擦剂等领域,但该类化合物的设计还有很长的路等待探索。
在本专利中,我们尝试对腰果酚进行结构改造,在之前制得产物腰果酚低聚醚酯的基础上,发现对其酚羟基的改造可以进一步优化,即制备成低聚酯。因低聚酯与环氧基团都对PVC的自由基团分离有较好效果,故其效果制得期待。
发明内容
发明目的:本发明所要解决的技术问题是针对现有技术中邻苯二甲酸酯类增塑剂易迁出塑料制品而污染环境、危害人体健康等问题,提供一种环氧腰果酚低聚酯型增塑剂,并提供该增塑剂的制备方法和应用。
为了解决上述技术问题,本发明公开了如式Ⅰ所示的环氧腰果酚低聚酯型增塑剂,
其中,n为选自1~9的整数;
其中,R1选自R1-1、R1-2、R1-3、R1-4;
其中,R2选自R2-1、R2-2、R2-3;
其中,所述环氧腰果酚低聚酯型增塑剂的环氧值为2.23%~2.46%。
上述的环氧腰果酚低聚酯型增塑剂的制备方法,其特征在于,包括如下步骤:
(1)将腰果酚、金属化合物催化剂和内酯溶于第一溶剂中反应,得到腰果酚低聚酯;
(2)将步骤(1)所得的腰果酚低聚酯与催化剂、冰醋酸和酸酐反应,得到封端的腰果酚低聚酯;
(3)将步骤(2)所得的封端的腰果酚低聚酯和过氧酸溶于第二溶剂中反应,得到环氧腰果酚低聚酯型增塑剂。
步骤(1)中,所述的金属化合物催化剂为辛酸亚锡、醋酸亚锡、烷基铝和氯化锌中的任意一种;所述的内脂为ε-己内酯、γ-丁内酯、δ-戊内酯等中的任意一种,优选ε-己内酯;所述的第一溶剂为有机溶剂,具体为苯、甲苯、环己烷中的任意一种;腰果酚、金属化合物催化剂和内酯的摩尔比为1:(0.1~0.2):(4~7);第一溶剂用量为腰果酚、金属化合物催化剂和内酯总质量的6~7倍。
其中,所述的内酯使用前需要经过氢化钙干燥并减压蒸馏;所述的甲苯为经金属钠精制过的甲苯溶液。
步骤(1)中,所述的反应为于氮气保护下进行的聚合反应,反应的时间为20~26h,温度为90~130℃;其中,反应的时间优选24h。
其中,所述的反应可加入搅拌,以增加物质之间的传质作用,其对搅拌速率没有具体的要求;所述的反应优选回流反应。
步骤(1)中,反应结束后,用正己烷洗涤反应液、干燥得到粗产品,将粗产品于索氏提取器中用丙酮提取,干燥得腰果酚低聚酯;其中,所述的索氏提取为用丙酮于56~60℃下提取5~10h。
步骤(2)中,所述的催化剂为柠檬酸、高氯酸、吡啶和乳酸中的任意一种;腰果酚低聚酯与催化剂的摩尔比为1:(1~2);冰醋酸和酸酐的体积比为1:3;腰果酚低聚酯与冰醋酸的质量体积比为0.05~1.2g/mL。
其中,所述的催化剂优选浓度为0.2mol/L的柠檬酸;所述腰果酚低聚酯与冰醋酸的质量体积比优选0.09g/mL。
步骤(2)中,所述的反应为70~100℃下回流反应2~5h;其中,回流反应时间优选4h。
步骤(2)中,反应结束后,用大量的清水洗产物至中性,放入烘箱干燥24h后得到封端的腰果酚低聚酯。
步骤(3)中,所述的过氧酸为间氯过氧苯甲酸、双氧水和叔丁基过氧化氢中的任意一种;所述的第二溶剂为有机溶剂,具体为二氯甲烷或甲酸;封端的腰果酚低聚酯、过氧酸和有机溶剂的摩尔比为1:(1~2):(15~20);其中,所述的第二溶剂具有溶解稀释的作用。
步骤(3)中,所述的反应为0~70℃反应0.5~3h,为防止反应过于剧烈而引发危险,过氧酸需要少量多次加入。
步骤(3)中,反应结束后,将产物过滤,将滤液用饱和亚硫酸钠、饱和碳酸氢钠和蒸馏水洗涤,得到有机相和水相,将有机相经无水硫酸钠干燥,过滤,滤液经减压旋蒸除去溶剂,得到环氧腰果酚低聚酯型增塑剂。
上述环氧腰果酚低聚酯型增塑剂的制备方法以腰果酚和内酯为原料,加入金属化合物催化剂在甲苯环境下开环聚合,并用酸酐封端,之后通过低温原位环氧化反应制得环氧腰果酚低聚酯。
以ε-己内酯为例,上述环氧腰果酚低聚酯型增塑剂的具体合成路线,反应结构式如下:
上述环氧腰果酚低聚酯型增塑剂在制备PVC制品中的应用。
其中,所述的应用为提高PVC制品的抗低温冲击性能、抗撕裂强度和延长PVC制品的寿命。
本发明通过将腰果酚的羟基改造为聚酯链,并对烷基链上的不饱和键进行环氧化改造,使其既具有环氧型增塑剂可以吸收聚氯乙烯中因光和热降解出来的氯化氢,阻止PVC的连续降解,起到延长PVC制品使用寿命的作用,又有聚酯型增塑剂增强PVC制品的抗低温冲击和抗撕裂强度的优点。
本发明以可再生资源腰果酚为原料,得到了一种低毒的新型环保增塑剂,以降低大批量塑料加工对环境带来的危害,并丰富了食品加工废料腰果油的使用,减少浪费。
有益效果:与现有技术相比,本发明具有如下的优势:
(1)本发明的原料腰果酚是食品加工副产物,易于提取、价格低廉、可再生,降低了增塑剂行业对石化产品的依赖,保护了环境和人类健康。
(2)本发明以可再生资源腰果酚为原料,得到了一种低毒的新型环保增塑剂,以降低大批量塑料加工对环境带来的危害,并丰富了食品加工废料腰果油的使用,减少浪费。
(3)本发明以腰果酚为原料制备出安全环保的生物增塑剂,其包含了环氧型增塑剂和聚酯型增塑剂的优点,让PVC制品既有突出的抗低温冲击和非常高的抗撕裂强度能力,又可以续收聚氯乙烯中因光和热降解出来的氯化氢,阻止PVC的连续降解,起到延长PVC制品使用寿命的作用。
附图说明
图1为PVC样品的TGA曲线。
图2为实施例1中为步骤1产物的氢谱、碳谱图。
图3为实施例1中步骤2产物的氢谱、碳谱。
图4为实施例1中步骤3产物的氢谱、碳谱。
具体实施方式
根据下述实施例,可以更好地理解本发明。然而,本领域的技术人员容易理解,实施例所描述的内容仅用于说明本发明,而不应当也不会限制权利要求书中所详细描述的本发明。
本发明中环氧值的检测方法参照GB/T 1677-2008《增塑剂环氧值的测定》
实施例1:
步骤一:将5g腰果酚、46.79gε-己内酯、0.997g辛酸亚锡和80mL精制过的甲苯置于一个100mL圆底烧瓶中,在氮气保护下磁力搅拌,于120℃下回流24h。反应完毕后产物在100mL正己烷中沉淀,过滤,然后用正己烷洗涤,干燥。之后把干燥产物放置于索氏提取器中用丙酮于60℃下连续提取6h,干燥,得到腰果酚低聚酯。其核磁谱图见图2。
步骤二:将4.5g腰果酚低聚酯、50mL冰醋酸、150mL乙酸酐和15mL(0.2mol/L)柠檬酸加到烧瓶中,在70℃下冷凝回流1h后,倒入分液漏斗中用大量水清洗至中性,干燥,得到封端的腰果酚低聚酯。其核磁谱图见图3。
步骤三:将3.6g封端的腰果酚低聚酯加入到烧瓶中,1.5g间氯过氧苯甲酸溶于100mL二氯甲烷后分三次加入到烧瓶中,在25℃下反应3h。反应结束后,粗产物经过滤后,将滤液用饱和亚硫酸钠、饱和碳酸氢钠和蒸馏水洗涤,得到有机相和水相,其中有机相经无水硫酸钠干燥,过滤,滤液经减压旋蒸除去溶剂,得到环氧腰果酚低聚醚酯增塑剂成品。产品为黄色固体,环氧值2.46%。其核磁谱图见图4。
实施例2:
步骤一:将5g腰果酚、47.92gε-己内酯、0.997g辛酸亚锡和80mL精制过的甲苯置于一个100mL圆底烧瓶中,在氮气保护下磁力搅拌,于120℃下回流24h。反应完毕后产物在100mL正己烷中沉淀,过滤,然后用正己烷洗涤,干燥。之后把干燥产物放置于索氏提取器中用丙酮于60℃下连续提取6h,干燥。
步骤二:将4.5g腰果酚低聚酯、50mL冰醋酸、150mL乙酸酐和16mL(0.2mol/L)柠檬酸加到烧瓶中,在70℃下冷凝回流1h后,倒入分液漏斗中用大量水清洗至中性,干燥,得到封端的腰果酚低聚酯。
步骤三:将3.6g封端的腰果酚低聚酯加入到烧瓶中,1.7g间氯过氧苯甲酸溶于100mL二氯甲烷后分三次加入到烧瓶中,在25℃下反应3h。反应结束后,粗产物经过滤后将滤液用饱和亚硫酸钠、饱和碳酸氢钠和蒸馏水洗涤,得到有机相和水相,其中有机相经无水硫酸钠干燥,过滤,滤液经减压旋蒸除去溶剂,得到环氧腰果酚低聚醚酯增塑剂成品。产品为黄色固体,环氧值2.38%。
实施例3:
步骤一:将5g腰果酚、42.36gε-己内酯、0.997g辛酸亚锡和80mL精制过的甲苯置于一个100mL圆底烧瓶中,在氮气保护下磁力搅拌,于120℃下回流24h。反应完毕后产物在100mL正己烷中沉淀,过滤,然后用正己烷洗涤,干燥。之后把干燥产物放置于索氏提取器中用丙酮于60℃下连续提取6h,干燥。
步骤二:将4.5g腰果酚低聚酯、50mL冰醋酸、150mL乙酸酐和17mL(0.2mol/L)柠檬酸加到烧瓶中,在70℃下冷凝回流1h后,倒入分液漏斗中用大量水清洗至中性,干燥,得到封端的腰果酚低聚酯。
步骤三:将3.6g封端的腰果酚低聚酯加入到烧瓶中,1.4g间氯过氧苯甲酸溶于100mL二氯甲烷后分三次加入到烧瓶中,在25℃下反应3h。反应结束后,粗产物经过滤后将滤液用饱和亚硫酸钠、饱和碳酸氢钠和蒸馏水洗涤,得到有机相和水相,其中有机相经无水硫酸钠干燥,过滤,滤液经减压旋蒸除去溶剂,得到环氧腰果酚低聚醚酯增塑剂成品。产品为黄色固体,环氧值2.45%。
实施例4:
步骤一:将5g腰果酚、49.52gε-己内酯、0.997g辛酸亚锡和80mL精制过的甲苯置于一个100mL圆底烧瓶中,在氮气保护下磁力搅拌,于120℃下回流24h。反应完毕后产物在100mL正己烷中沉淀,过滤,然后用正己烷洗涤,干燥。之后把干燥产物放置于索氏提取器中用丙酮于58℃下连续提取6h,干燥。
步骤二:将4.5g腰果酚低聚酯、50mL冰醋酸、150mL乙酸酐和15mL(0.2mol/L)柠檬酸加到烧瓶中,在70℃下冷凝回流1h后,倒入分液漏斗中用大量水清洗至中性,干燥,得到封端的腰果酚低聚酯。
步骤三:将3.6g封端的腰果酚低聚酯加入到烧瓶中,1.3g间氯过氧苯甲酸溶于100mL二氯甲烷后分三次加入到烧瓶中,在25℃下反应3h。反应结束后,粗产物经过滤后将滤液用饱和亚硫酸钠、饱和碳酸氢钠和蒸馏水洗涤,得到有机相和水相,其中有机相经无水硫酸钠干燥,过滤,滤液经减压旋蒸除去溶剂,得到环氧腰果酚低聚醚酯增塑剂成品。产品为黄色固体,环氧值2.38%。
实施例5:
步骤一:将5g腰果酚、52.36gε-己内酯、0.997g辛酸亚锡和80mL精制过的甲苯置于一个100mL圆底烧瓶中,在氮气保护下磁力搅拌,于120℃下回流24h。反应完毕后产物在100mL正己烷中沉淀,过滤,然后用正己烷洗涤,干燥。之后把干燥产物放置于索氏提取器中用丙酮于58℃下连续提取6h,干燥。
步骤二:将4.5g腰果酚低聚酯、50mL冰醋酸、150mL乙酸酐和15mL(0.2mol/L)柠檬酸加到烧瓶中,在70℃下冷凝回流1h后,倒入分液漏斗中用大量水清洗至中性,干燥,得到封端的腰果酚低聚酯。
步骤三:将3.6g封端的腰果酚低聚酯加入到烧瓶中,1.6g间氯过氧苯甲酸溶于100mL二氯甲烷后分三次加入到烧瓶中,在25℃下反应3h。反应结束后,粗产物经过滤后将滤液用饱和亚硫酸钠、饱和碳酸氢钠和蒸馏水洗涤,得到有机相和水相,其中有机相经无水硫酸钠干燥,过滤,滤液经减压旋蒸除去溶剂,得到环氧腰果酚低聚醚酯增塑剂成品。产品为黄色固体,环氧值2.23%。
实施例6:
将实施例1中合成的增塑剂环氧腰果酚低聚醚酯(ECO)与对苯二甲酸二辛酯(DOTP)复配,用于增塑PVC,共混物的配方如表1所示。将PVC粉末、增塑剂及热稳定剂混合高速搅拌均匀后,再用转矩流变仪密炼,最后通过平板硫化机压制成一定厚度的PVC膜,用于拉伸性能测试。表2为不同配方的PVC样品的力学性能测试结果。由表可知,随着环氧腰果酚低聚酯增塑剂含量的增加,PVC样品的拉伸强度有所增加,表明该增塑剂与PVC的相容性优于DOP与PVC的相容性,可以赋予PVC制品良好的柔韧性。
表1 PVC制品配方
表2 PVC制品的力学性能测试结果
实施例7:
将环氧腰果酚低聚酯(ECO)、腰果酚低聚酯(CO)、对苯二甲酸二辛酯(DOTP)、邻苯二甲酸二异壬酯(DINP)增塑剂与PVC和辅料按表3中的配方混合制备成测试所需的样条,制备方法同实施例6。
为了考察增塑剂对PVC样品热稳定性的影响,含有不同增塑剂的PVC样品在氮气氛围及10℃/min升温速率下的TGA曲线如图1所示。下表中列示了TGA曲线的特征温度。结合图表分析,可以看出,样品的热分解主要分为两个阶段。第一阶段,即在220~300℃温度范围内,热分解速率最快,该阶段主要是发生了PVC加热脱氯作用,即C-Cl键断裂,生成的Cl原子与邻近亚甲基上的H原子生成HCl,使得PVC链上形成双键,进一步诱发邻近的C-Cl键断裂,产生大量的Cl原子和大分子自由基,导致PVC的连续分解。第二阶段,即在300~600℃范围内,发生的主要是芳香化合物以及聚酯的热分解。
实验结果表明,与其他三种增塑剂体系相比,ECO/PVC在第一阶段的质量损失偏低,说明其具有较高的热稳定性。根据文献可知其原因是ECO中的环氧基团可以捕获PVC热解过程中生成的HCl,进而阻止PVC的连续分解,提高产品的热稳定性,进而延长其在室温及较高温情况下的使用寿命。
表3含不同增塑剂的PVC制品配方
表4热失重分析数据
本发明提供了一种环氧腰果酚低聚酯型增塑剂及其制备与应用的思路及方法,具体实现该技术方案的方法和途径很多,以上所述仅是本发明的优选实施方式,应当指出,对于本技术领域的普通技术人员来说,在不脱离本发明原理的前提下,还可以做出若干改进和润饰,这些改进和润饰也应视为本发明的保护范围。本实施例中未明确的各组成部分均可用现有技术加以实现。
Claims (10)
2.权利要求1所述环氧腰果酚低聚酯型增塑剂的制备方法,其特征在于,包括如下步骤:
(1)将腰果酚、金属化合物催化剂和内酯溶于第一溶剂中反应,得到腰果酚低聚酯;
(2)将步骤(1)所得的腰果酚低聚酯与催化剂、冰醋酸和酸酐反应,得到封端的腰果酚低聚酯;
(3)将步骤(2)所得的封端的腰果酚低聚酯和过氧酸溶于第二溶剂中反应,得到环氧腰果酚低聚酯型增塑剂。
3.根据权利要求2所述的环氧腰果酚低聚酯型增塑剂的制备方法,其特征在于,步骤(1)中,所述的金属化合物催化剂为辛酸亚锡、醋酸亚锡、烷基铝和氯化锌中的任意一种;所述的内脂为ε-己内酯、γ-丁内酯、δ-戊内酯等中的任意一种;所述的第一溶剂为苯、甲苯、环己烷中的任意一种;腰果酚、金属化合物催化剂和内酯的摩尔比为1:(0.1~0.2):(4~7);第一溶剂用量为腰果酚、金属化合物催化剂和内酯总质量的6~7倍。
4.根据权利要求2所述的环氧腰果酚低聚酯型增塑剂的制备方法,其特征在于,步骤(1)中,所述的反应为于氮气保护下进行反应,反应的时间为20~26h,温度为90~130℃。
5.根据权利要求2所述的环氧腰果酚低聚酯型增塑剂的制备方法,其特征在于,步骤(1)中,反应结束后,用正己烷洗涤反应液、干燥得到粗产品,将粗产品于索氏提取器中用丙酮提取,干燥得腰果酚低聚酯。
6.根据权利要求2所述的环氧腰果酚低聚酯型增塑剂的制备方法,其特征在于,步骤(2)中,所述的催化剂为柠檬酸、高氯酸、吡啶和乳酸中的任意一种;腰果酚低聚酯与催化剂的摩尔比为1:(1~2);冰醋酸和酸酐的体积比为1:3;腰果酚低聚酯与冰醋酸的质量体积比为0.05~1.2g/mL。
7.根据权利要求2所述的环氧腰果酚低聚酯型增塑剂的制备方法,其特征在于,步骤(2)中,所述的反应为70~100℃下回流反应2~5h;反应结束后,水洗产物至中性,干燥后得到封端的腰果酚低聚酯。
8.根据权利要求2所述的环氧腰果酚低聚酯型增塑剂的制备方法,其特征在于,步骤(3)中,所述的过氧酸为间氯过氧苯甲酸、双氧水和叔丁基过氧化氢中的任意一种;所述的第二溶剂为二氯甲烷或甲酸;封端的腰果酚低聚酯、过氧酸和有机溶剂的摩尔比为1:(1~2):(15~20)。
9.根据权利要求2所述的环氧腰果酚低聚酯型增塑剂的制备方法,其特征在于,步骤(3)中,所述的反应为0~70℃反应0.5~3h;反应结束后,将产物过滤,将滤液用饱和亚硫酸钠、饱和碳酸氢钠和蒸馏水洗涤,得到有机相和水相,将有机相经无水硫酸钠干燥,过滤,滤液经减压旋蒸除去溶剂,得到环氧腰果酚低聚酯型增塑剂。。
10.权利要求1所述环氧腰果酚低聚酯型增塑剂在制备PVC制品中的应用;
其中,所述应用为环氧腰果酚低聚酯型增塑剂能提高PVC制品的抗低温冲击性能、抗撕裂强度和延长PVC制品的寿命。
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CN202010091020.XA CN111253341B (zh) | 2020-02-13 | 2020-02-13 | 一种环氧腰果酚低聚酯型增塑剂及其制备与应用 |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CN202010091020.XA CN111253341B (zh) | 2020-02-13 | 2020-02-13 | 一种环氧腰果酚低聚酯型增塑剂及其制备与应用 |
Publications (2)
Publication Number | Publication Date |
---|---|
CN111253341A true CN111253341A (zh) | 2020-06-09 |
CN111253341B CN111253341B (zh) | 2021-04-20 |
Family
ID=70951073
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
CN202010091020.XA Active CN111253341B (zh) | 2020-02-13 | 2020-02-13 | 一种环氧腰果酚低聚酯型增塑剂及其制备与应用 |
Country Status (1)
Country | Link |
---|---|
CN (1) | CN111253341B (zh) |
Cited By (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN113881102A (zh) * | 2021-11-09 | 2022-01-04 | 北京工商大学 | 一种环氧腰果酚酯生物基增塑剂的制备方法及其产品和应用 |
CN114605259A (zh) * | 2022-02-24 | 2022-06-10 | 江苏麒祥高新材料有限公司 | 改性腰果油、橡胶增塑剂及其制备方法和应用 |
WO2023127609A1 (ja) * | 2021-12-27 | 2023-07-06 | 日本ゼオン株式会社 | 可塑剤組成物、樹脂組成物、樹脂成形体および積層体 |
Citations (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN102634000A (zh) * | 2012-04-27 | 2012-08-15 | 郑州大学 | 一种嵌段型聚酯分散剂及其制备方法 |
CN103342834A (zh) * | 2013-07-24 | 2013-10-09 | 中国林业科学研究院林产化学工业研究所 | 一种环氧腰果酚基乙酸酯增塑剂及其制备方法 |
US20190077815A1 (en) * | 2017-09-12 | 2019-03-14 | Cardolite Corporation | Compositions, synthesis, and uses of hydrolyzable silane modified cashew nut shell liquid derivatives |
-
2020
- 2020-02-13 CN CN202010091020.XA patent/CN111253341B/zh active Active
Patent Citations (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN102634000A (zh) * | 2012-04-27 | 2012-08-15 | 郑州大学 | 一种嵌段型聚酯分散剂及其制备方法 |
CN103342834A (zh) * | 2013-07-24 | 2013-10-09 | 中国林业科学研究院林产化学工业研究所 | 一种环氧腰果酚基乙酸酯增塑剂及其制备方法 |
US20190077815A1 (en) * | 2017-09-12 | 2019-03-14 | Cardolite Corporation | Compositions, synthesis, and uses of hydrolyzable silane modified cashew nut shell liquid derivatives |
Cited By (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN113881102A (zh) * | 2021-11-09 | 2022-01-04 | 北京工商大学 | 一种环氧腰果酚酯生物基增塑剂的制备方法及其产品和应用 |
WO2023127609A1 (ja) * | 2021-12-27 | 2023-07-06 | 日本ゼオン株式会社 | 可塑剤組成物、樹脂組成物、樹脂成形体および積層体 |
CN114605259A (zh) * | 2022-02-24 | 2022-06-10 | 江苏麒祥高新材料有限公司 | 改性腰果油、橡胶增塑剂及其制备方法和应用 |
Also Published As
Publication number | Publication date |
---|---|
CN111253341B (zh) | 2021-04-20 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
CN111253341B (zh) | 一种环氧腰果酚低聚酯型增塑剂及其制备与应用 | |
CN111269459B (zh) | 一种环氧腰果酚醚酯增塑剂及其制备方法与应用 | |
Ardhyananta et al. | Performance enhancement of polybenzoxazine by hybridization with polysiloxane | |
JP5398650B2 (ja) | 新規なデヒドロアビエチン酸重合体 | |
KR101570386B1 (ko) | 에폭시계 에스테르 화합물을 포함한 복합 가소제 조성물 및 이를 이용한 고분자 수지 조성물 | |
JP5436251B2 (ja) | デヒドロアビエチン酸重合体、成形体、デヒドロアビエチン酸重合体の製造方法、及びデヒドロアビエチン酸化合物 | |
CN104774587B (zh) | 一种高粘度强耐热的改性有机硅树脂粘胶剂及其制备方法 | |
CN113004506A (zh) | 一种耐热耐迁移的环保增塑剂的制备方法及其应用 | |
JP5300680B2 (ja) | 新規なアビエタン重合体 | |
CN113201127A (zh) | 聚硅氧烷-聚碳酸酯共聚物、制造方法及聚碳酸酯树脂 | |
CN111533889A (zh) | 一种高热稳定性的耐迁移性聚酯增塑剂及其制备方法 | |
Yao et al. | Preparation of cardanol based epoxy plasticizer by click chemistry and its action on poly (vinyl chloride) | |
CN107216250B (zh) | 一种利用聚对苯二甲酸乙二醇酯废料制备对苯二甲酸二异辛酯的方法 | |
CN112794828B (zh) | 一种环氧化碳酸二腰果酚酯型增塑剂 | |
CN101659677B (zh) | 三聚膦腈环氧树脂及其制备方法 | |
CN113248787A (zh) | 一种增塑剂及其制备方法和应用 | |
CN102822226A (zh) | 制备二乙烯基芳烃二氧化物的方法 | |
CN111718314B (zh) | 一种植物油基耐寒增塑剂的制备方法及其应用 | |
CN112920394B (zh) | 一种乳酸基环保增塑剂的制备方法及其应用 | |
CN113683508B (zh) | 一种香草酸酯环保增塑剂及其制备方法 | |
JP4843999B2 (ja) | 脂環族二価アルコールエステル | |
CN108530681B (zh) | 一种提高环氧乙酰蓖麻油酸甲酯增塑剂与pvc树脂相容性的方法 | |
CN108641019B (zh) | 一种松香基硫醇化的聚氯乙烯梳状聚合物及其制备方法和应用 | |
CN107311897A (zh) | 2,4‑二叔丁基‑6‑正辛基硫亚甲基苯酚及其制备工艺 | |
CN110746589B (zh) | 一种乌桕油基超支化聚酯增塑剂及其制备方法 |
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 |