CN109867930A - Resistance to migration environment-friendlyplasticizer plasticizer of one kind and preparation method thereof - Google Patents
Resistance to migration environment-friendlyplasticizer plasticizer of one kind and preparation method thereof Download PDFInfo
- Publication number
- CN109867930A CN109867930A CN201910125189.XA CN201910125189A CN109867930A CN 109867930 A CN109867930 A CN 109867930A CN 201910125189 A CN201910125189 A CN 201910125189A CN 109867930 A CN109867930 A CN 109867930A
- Authority
- CN
- China
- Prior art keywords
- mass ratio
- added
- resistance
- plasticizer
- take
- 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.)
- Pending
Links
- 239000004014 plasticizer Substances 0.000 title claims abstract description 98
- 230000005012 migration Effects 0.000 title claims abstract description 54
- 238000013508 migration Methods 0.000 title claims abstract description 54
- 238000002360 preparation method Methods 0.000 title claims abstract description 36
- 239000000654 additive Substances 0.000 claims abstract description 78
- 230000000996 additive effect Effects 0.000 claims abstract description 69
- 230000000694 effects Effects 0.000 claims abstract description 28
- 239000002253 acid Substances 0.000 claims abstract description 23
- 238000007334 copolymerization reaction Methods 0.000 claims abstract description 22
- 239000003054 catalyst Substances 0.000 claims abstract description 21
- 230000003197 catalytic effect Effects 0.000 claims abstract description 14
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 8
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims abstract description 8
- 229910052799 carbon Inorganic materials 0.000 claims abstract description 8
- 238000004440 column chromatography Methods 0.000 claims abstract description 8
- 239000000741 silica gel Substances 0.000 claims abstract description 8
- 229910002027 silica gel Inorganic materials 0.000 claims abstract description 8
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 3
- 239000001257 hydrogen Substances 0.000 claims abstract description 3
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 claims description 163
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 72
- 239000000203 mixture Substances 0.000 claims description 56
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 36
- 229910052757 nitrogen Inorganic materials 0.000 claims description 36
- 239000000463 material Substances 0.000 claims description 35
- 238000003756 stirring Methods 0.000 claims description 33
- 238000002156 mixing Methods 0.000 claims description 30
- 238000010792 warming Methods 0.000 claims description 20
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 18
- WERYXYBDKMZEQL-UHFFFAOYSA-N butane-1,4-diol Chemical compound OCCCCO WERYXYBDKMZEQL-UHFFFAOYSA-N 0.000 claims description 18
- 239000003795 chemical substances by application Substances 0.000 claims description 18
- 238000005292 vacuum distillation Methods 0.000 claims description 17
- 229920005862 polyol Polymers 0.000 claims description 14
- 230000003213 activating effect Effects 0.000 claims description 13
- 150000003077 polyols Chemical class 0.000 claims description 13
- 238000004321 preservation Methods 0.000 claims description 13
- 239000007858 starting material Substances 0.000 claims description 13
- WTEOIRVLGSZEPR-UHFFFAOYSA-N boron trifluoride Chemical compound FB(F)F WTEOIRVLGSZEPR-UHFFFAOYSA-N 0.000 claims description 12
- XLJMAIOERFSOGZ-UHFFFAOYSA-M cyanate Chemical compound [O-]C#N XLJMAIOERFSOGZ-UHFFFAOYSA-M 0.000 claims description 12
- JHIVVAPYMSGYDF-UHFFFAOYSA-N cyclohexanone Chemical compound O=C1CCCCC1 JHIVVAPYMSGYDF-UHFFFAOYSA-N 0.000 claims description 12
- 238000002390 rotary evaporation Methods 0.000 claims description 12
- FYSNRJHAOHDILO-UHFFFAOYSA-N thionyl chloride Chemical compound ClS(Cl)=O FYSNRJHAOHDILO-UHFFFAOYSA-N 0.000 claims description 12
- -1 2-Ethylhexyl Alcohols Chemical class 0.000 claims description 10
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 claims description 8
- 238000001035 drying Methods 0.000 claims description 8
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 7
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 7
- 239000008367 deionised water Substances 0.000 claims description 7
- 229910021641 deionized water Inorganic materials 0.000 claims description 7
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 7
- XNWFRZJHXBZDAG-UHFFFAOYSA-N 2-METHOXYETHANOL Chemical compound COCCO XNWFRZJHXBZDAG-UHFFFAOYSA-N 0.000 claims description 6
- 229910015900 BF3 Inorganic materials 0.000 claims description 6
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 claims description 6
- UKLDJPRMSDWDSL-UHFFFAOYSA-L [dibutyl(dodecanoyloxy)stannyl] dodecanoate Chemical compound CCCCCCCCCCCC(=O)O[Sn](CCCC)(CCCC)OC(=O)CCCCCCCCCCC UKLDJPRMSDWDSL-UHFFFAOYSA-L 0.000 claims description 6
- 239000004359 castor oil Substances 0.000 claims description 6
- 235000019438 castor oil Nutrition 0.000 claims description 6
- 229960000935 dehydrated alcohol Drugs 0.000 claims description 6
- 239000012975 dibutyltin dilaurate Substances 0.000 claims description 6
- ZEMPKEQAKRGZGQ-XOQCFJPHSA-N glycerol triricinoleate Natural products CCCCCC[C@@H](O)CC=CCCCCCCCC(=O)OC[C@@H](COC(=O)CCCCCCCC=CC[C@@H](O)CCCCCC)OC(=O)CCCCCCCC=CC[C@H](O)CCCCCC ZEMPKEQAKRGZGQ-XOQCFJPHSA-N 0.000 claims description 6
- 125000004836 hexamethylene group Chemical group [H]C([H])([*:2])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[*:1] 0.000 claims description 6
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical class O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 claims description 6
- 229920000151 polyglycol Polymers 0.000 claims description 6
- 239000010695 polyglycol Substances 0.000 claims description 6
- 229920001228 polyisocyanate Polymers 0.000 claims description 6
- 239000005056 polyisocyanate Substances 0.000 claims description 6
- 229920006389 polyphenyl polymer Polymers 0.000 claims description 6
- 229920001451 polypropylene glycol Polymers 0.000 claims description 6
- 230000001376 precipitating effect Effects 0.000 claims description 6
- 238000000034 method Methods 0.000 claims description 5
- SRPWOOOHEPICQU-UHFFFAOYSA-N trimellitic anhydride Chemical compound OC(=O)C1=CC=C2C(=O)OC(=O)C2=C1 SRPWOOOHEPICQU-UHFFFAOYSA-N 0.000 claims description 5
- MUTGBJKUEZFXGO-OLQVQODUSA-N (3as,7ar)-3a,4,5,6,7,7a-hexahydro-2-benzofuran-1,3-dione Chemical compound C1CCC[C@@H]2C(=O)OC(=O)[C@@H]21 MUTGBJKUEZFXGO-OLQVQODUSA-N 0.000 claims description 4
- QWGRWMMWNDWRQN-UHFFFAOYSA-N 2-methylpropane-1,3-diol Chemical compound OCC(C)CO QWGRWMMWNDWRQN-UHFFFAOYSA-N 0.000 claims description 4
- BWDBEAQIHAEVLV-UHFFFAOYSA-N 6-methylheptan-1-ol Chemical compound CC(C)CCCCCO BWDBEAQIHAEVLV-UHFFFAOYSA-N 0.000 claims description 4
- 239000006185 dispersion Substances 0.000 claims description 4
- 235000011187 glycerol Nutrition 0.000 claims description 4
- 229940100573 methylpropanediol Drugs 0.000 claims description 4
- 150000005208 1,4-dihydroxybenzenes Chemical class 0.000 claims description 3
- KDYFGRWQOYBRFD-UHFFFAOYSA-N Succinic acid Natural products OC(=O)CCC(O)=O KDYFGRWQOYBRFD-UHFFFAOYSA-N 0.000 claims description 3
- 229960004063 propylene glycol Drugs 0.000 claims description 3
- DCKVNWZUADLDEH-UHFFFAOYSA-N sec-butyl acetate Chemical compound CCC(C)OC(C)=O DCKVNWZUADLDEH-UHFFFAOYSA-N 0.000 claims description 3
- 230000008859 change Effects 0.000 claims description 2
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims 2
- LBLYYCQCTBFVLH-UHFFFAOYSA-N 2-Methylbenzenesulfonic acid Chemical compound CC1=CC=CC=C1S(O)(=O)=O LBLYYCQCTBFVLH-UHFFFAOYSA-N 0.000 claims 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims 1
- 150000008065 acid anhydrides Chemical class 0.000 claims 1
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 claims 1
- 239000003549 soybean oil Substances 0.000 claims 1
- 235000012424 soybean oil Nutrition 0.000 claims 1
- 239000011347 resin Substances 0.000 abstract description 19
- 229920005989 resin Polymers 0.000 abstract description 19
- 239000011159 matrix material Substances 0.000 abstract description 15
- 239000002994 raw material Substances 0.000 abstract description 8
- 239000000126 substance Substances 0.000 abstract description 7
- JOXIMZWYDAKGHI-UHFFFAOYSA-N toluene-4-sulfonic acid Chemical compound CC1=CC=C(S(O)(=O)=O)C=C1 JOXIMZWYDAKGHI-UHFFFAOYSA-N 0.000 abstract description 7
- 230000032050 esterification Effects 0.000 abstract description 3
- 238000005886 esterification reaction Methods 0.000 abstract description 3
- 238000004383 yellowing Methods 0.000 abstract description 3
- 238000009792 diffusion process Methods 0.000 abstract description 2
- 125000004185 ester group Chemical group 0.000 abstract description 2
- 230000001590 oxidative effect Effects 0.000 abstract description 2
- 150000002148 esters Chemical class 0.000 description 9
- 239000000047 product Substances 0.000 description 9
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 6
- BJQHLKABXJIVAM-UHFFFAOYSA-N bis(2-ethylhexyl) phthalate Chemical compound CCCCC(CC)COC(=O)C1=CC=CC=C1C(=O)OCC(CC)CCCC BJQHLKABXJIVAM-UHFFFAOYSA-N 0.000 description 6
- ZSIAUFGUXNUGDI-UHFFFAOYSA-N hexan-1-ol Chemical compound CCCCCCO ZSIAUFGUXNUGDI-UHFFFAOYSA-N 0.000 description 6
- 239000012188 paraffin wax Substances 0.000 description 6
- HIXDQWDOVZUNNA-UHFFFAOYSA-N 2-(3,4-dimethoxyphenyl)-5-hydroxy-7-methoxychromen-4-one Chemical compound C=1C(OC)=CC(O)=C(C(C=2)=O)C=1OC=2C1=CC=C(OC)C(OC)=C1 HIXDQWDOVZUNNA-UHFFFAOYSA-N 0.000 description 5
- 235000010469 Glycine max Nutrition 0.000 description 5
- 244000068988 Glycine max Species 0.000 description 5
- 239000012752 auxiliary agent Substances 0.000 description 5
- 230000000052 comparative effect Effects 0.000 description 5
- 239000003921 oil Substances 0.000 description 5
- 235000019198 oils Nutrition 0.000 description 5
- 239000004033 plastic Substances 0.000 description 5
- 229920003023 plastic Polymers 0.000 description 5
- 229920000642 polymer Polymers 0.000 description 5
- MQIUGAXCHLFZKX-UHFFFAOYSA-N Di-n-octyl phthalate Chemical compound CCCCCCCCOC(=O)C1=CC=CC=C1C(=O)OCCCCCCCC MQIUGAXCHLFZKX-UHFFFAOYSA-N 0.000 description 4
- 150000001875 compounds Chemical class 0.000 description 4
- 230000007613 environmental effect Effects 0.000 description 4
- 235000013305 food Nutrition 0.000 description 4
- 238000012545 processing Methods 0.000 description 4
- KNDQHSIWLOJIGP-UMRXKNAASA-N (3ar,4s,7r,7as)-rel-3a,4,7,7a-tetrahydro-4,7-methanoisobenzofuran-1,3-dione Chemical compound O=C1OC(=O)[C@@H]2[C@H]1[C@]1([H])C=C[C@@]2([H])C1 KNDQHSIWLOJIGP-UMRXKNAASA-N 0.000 description 3
- 239000004803 Di-2ethylhexylphthalate Substances 0.000 description 3
- YCIMNLLNPGFGHC-UHFFFAOYSA-N catechol Chemical compound OC1=CC=CC=C1O YCIMNLLNPGFGHC-UHFFFAOYSA-N 0.000 description 3
- 102100035474 DNA polymerase kappa Human genes 0.000 description 2
- 101710108091 DNA polymerase kappa Proteins 0.000 description 2
- 235000019482 Palm oil Nutrition 0.000 description 2
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 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
- 239000003995 emulsifying agent Substances 0.000 description 2
- 239000005556 hormone Substances 0.000 description 2
- 229940088597 hormone Drugs 0.000 description 2
- 230000006872 improvement Effects 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 239000003595 mist Substances 0.000 description 2
- JMANVNJQNLATNU-UHFFFAOYSA-N oxalonitrile Chemical compound N#CC#N JMANVNJQNLATNU-UHFFFAOYSA-N 0.000 description 2
- 239000002540 palm oil Substances 0.000 description 2
- 229920000728 polyester Polymers 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- 239000002028 Biomass Substances 0.000 description 1
- KRKNYBCHXYNGOX-UHFFFAOYSA-K Citrate Chemical compound [O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O KRKNYBCHXYNGOX-UHFFFAOYSA-K 0.000 description 1
- PXGOKWXKJXAPGV-UHFFFAOYSA-N Fluorine Chemical compound FF PXGOKWXKJXAPGV-UHFFFAOYSA-N 0.000 description 1
- 206010028980 Neoplasm Diseases 0.000 description 1
- 229910019142 PO4 Inorganic materials 0.000 description 1
- 235000010489 acacia gum Nutrition 0.000 description 1
- 239000001785 acacia senegal l. willd gum Substances 0.000 description 1
- 125000001931 aliphatic group Chemical group 0.000 description 1
- 238000004873 anchoring Methods 0.000 description 1
- 150000001555 benzenes Chemical class 0.000 description 1
- 235000013361 beverage Nutrition 0.000 description 1
- 239000011230 binding agent Substances 0.000 description 1
- 238000009395 breeding Methods 0.000 description 1
- 230000001488 breeding effect Effects 0.000 description 1
- FPCJKVGGYOAWIZ-UHFFFAOYSA-N butan-1-ol;titanium Chemical compound [Ti].CCCCO.CCCCO.CCCCO.CCCCO FPCJKVGGYOAWIZ-UHFFFAOYSA-N 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 201000011510 cancer Diseases 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 238000005660 chlorination reaction Methods 0.000 description 1
- 238000010073 coating (rubber) Methods 0.000 description 1
- DOIRQSBPFJWKBE-UHFFFAOYSA-N dibutyl phthalate Chemical compound CCCCOC(=O)C1=CC=CC=C1C(=O)OCCCC DOIRQSBPFJWKBE-UHFFFAOYSA-N 0.000 description 1
- 201000010099 disease Diseases 0.000 description 1
- 208000037265 diseases, disorders, signs and symptoms Diseases 0.000 description 1
- 238000006073 displacement reaction Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 229910052731 fluorine Inorganic materials 0.000 description 1
- 239000011737 fluorine Substances 0.000 description 1
- 235000013373 food additive Nutrition 0.000 description 1
- 239000002778 food additive Substances 0.000 description 1
- 235000015203 fruit juice Nutrition 0.000 description 1
- 238000007306 functionalization reaction Methods 0.000 description 1
- 230000036541 health Effects 0.000 description 1
- 235000015094 jam Nutrition 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 230000004630 mental health Effects 0.000 description 1
- 125000001570 methylene group Chemical group [H]C([H])([*:1])[*:2] 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 231100000252 nontoxic Toxicity 0.000 description 1
- 230000003000 nontoxic effect Effects 0.000 description 1
- 230000000269 nucleophilic effect Effects 0.000 description 1
- 238000004806 packaging method and process Methods 0.000 description 1
- 239000002304 perfume Substances 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 1
- 239000010452 phosphate Substances 0.000 description 1
- XNGIFLGASWRNHJ-UHFFFAOYSA-N phthalic acid Chemical group OC(=O)C1=CC=CC=C1C(O)=O XNGIFLGASWRNHJ-UHFFFAOYSA-N 0.000 description 1
- 231100000614 poison Toxicity 0.000 description 1
- 230000007096 poisonous effect Effects 0.000 description 1
- 239000004814 polyurethane Substances 0.000 description 1
- 229920002635 polyurethane Polymers 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 239000003566 sealing material Substances 0.000 description 1
- 230000035945 sensitivity Effects 0.000 description 1
- 239000002893 slag Substances 0.000 description 1
- 238000000967 suction filtration Methods 0.000 description 1
- 230000008719 thickening Effects 0.000 description 1
- 231100000331 toxic Toxicity 0.000 description 1
- 230000002588 toxic effect Effects 0.000 description 1
- 125000005591 trimellitate group Chemical group 0.000 description 1
Landscapes
- Compositions Of Macromolecular Compounds (AREA)
Abstract
The invention discloses a kind of resistance to migration environment-friendlyplasticizer plasticizers and preparation method thereof, belong to Organic chemical products technical field.The present invention is swollen after resin matrix is added, so that the diffusion of plasticizer is also improved, is crosslinked so that being formed with resin, is enhanced plasticization effect.The catalyst that active carbon and column chromatography silica gel load is added carries out catalytic esterification, and the characteristic using p-methyl benzenesulfonic acid as non-oxidative strong acid is catalyzed, and the environmental-protecting performance of plasticizer during the preparation process is improved, so that obtained plasticizer performance boost.It is connected using hydrogen bond and anchors plasticizer and resin matrix, reduced the migration of plasticizer ester group and reduce the pollution of environment, weatherability is improved.The weatherability and yellowing resistance energy of resin matrix are improved using the Copolymerization activity object of introducing, are dispersed additive and are increased mobility and greasy property of the plasticizer during plasticising, improve plasticizing efficiency.The present invention solves that current plasticizer is easy to migrate, the problem of raw material environmental-protecting performance difference.
Description
Technical field
The invention belongs to Organic chemical products technical fields, and in particular to the resistance to migration environment-friendlyplasticizer plasticizer of one kind and its preparation
Method.
Background technique
Plasticiser, generally also referred to as plasticizer.Plasticizer is the high molecular material auxiliary agent being industrially widely used, in plastics
This substance is added in processing, its flexibility can be made to enhance, be easily worked, and legal can be used for industrial use.Manufacturer is a kind of
DINP, DNOP, DBP, DMP, DEP etc. are detected successively after common plasticizer DEHP() replace the mist generating agent of palm oil preparation also can
Generate thickening effect similar with emulsifier.But insider points out, the plasticisers such as DEHP, DINP are simultaneously not belonging to food perfume
Expect raw material.Therefore, DEHP cannot be not only added in food, or even not allowed using in food packaging." mist generating agent " is
A kind of kasher additive, is frequently used in the food such as fruit juice, jam, beverage, is by Arabic gum, emulsifier, palm
Oil and numerous food additives mixed are made.The molecular structure of certain plasticisers is similar to hormone, referred to as " Environmental Hormone ",
It is the poisonous chemical substance of Taiwan Environmental Protection Administration tubulation.If long-term consumption may cause breeding unsoundness, even cause monster, cancer
The danger of disease.Existing plasticizer effect is unstable, needs to reinforce, be more toxic, and is unfavorable for physical and mental health, pollutes environment.Its point
Minor structure has polar portion and nonpolar moiety, because plasticizer molecule can be inserted between the high-polymer molecule chain, weakens molecule
Between active force, increase the distance between the high-polymer molecule chain and activity space, increase the plasticity of high polymer, reduce high polymer plus
Work temperature, therefore plasticizer is added in plastic processing, its flexibility can be made to enhance, be easily worked, be widely used in height
Molecular material auxiliary agent.Conventional plasticizers usually used at present, the flexibility and elasticity of moulded products vary over,
Product quality is influenced, and makes product surface that there is viscosity.And conventional plasticizer weatherability is poor, and there are apparent offices for purposes
It is sex-limited.Chemical stability at plasticizer performance major criterion.People also increasingly increase the environmental requirement of plasticizer simultaneously.
Plasticizer is the auxiliary agent of PVC industry dosage maximum, most critical, while also sending out in fields such as rubber coating, binder, sealing materials
Important role is waved, is one of maximum auxiliary agent of yield in plastic applications, effect is the plastic of increase high-molecular compound
Property and flexibility, while reducing brittleness.
Product mainly based on phthalic ester plasticizer, accounts for about nearly the 90% of aggregate consumption in real consumption,
Middle DOP(dioctyl phthalate) account for about the 70% of aggregate consumption, the plasticizer yield of non-neighboring benzene class is less than 10%, and biology can
It degrades and few as the environment-friendlyplasticizer plasticizer product of raw material using biomass, is unable to satisfy PVC plastic processing industry to nontoxic, biological drop
The requirement of solution and the strong plasticizer of plasticization capacity.
Plasticizer is to confer to the functionalization auxiliary agent of polymer product flexibility and processability, especially in soft PVC
(PVC) it is had a wide range of applications in product.According to the difference of chemical structure, the plasticizer kind being put on sale so far mainly includes adjacent benzene
Dicarboxylic acid esters, aliphatic dibasic acid ester, trimellitate, polyol ester, citrate, phosphate, polyester, epoxyfatty acid
And its chemical structural types such as ester, wherein the production consumption of phthalic ester plasticizer is maximum, and it is total almost to account for entire plasticizer
70% or more of amount.However, limitation has been required since the 1990s in global range based on environment and safe and healthy reason
It is continuous using the cry of phthalic ester plasticizer, related environmental protection, health, sustainable phthalic ester plasticizer
Substitute developmental research report emerges one after another.
Summary of the invention
The technical problems to be solved by the invention: easy to migrate for current plasticizer, the problem of raw material environmental-protecting performance difference mentions
For a kind of resistance to migration environment-friendlyplasticizer plasticizer and preparation method thereof.
In order to solve the above technical problems, the present invention is using technical solution as described below:
A kind of resistance to migration environment-friendlyplasticizer plasticizer, including plasticiser additive, resistance to migration additive, dispersing additive；
The plasticizer additive the preparation method comprises the following steps: according to the mass fraction, taking 20 ~ 30 parts of acid starting materials, 30 ~ 50 parts of raw polyols, 3
~ 8 parts of 2-Ethylhexyl Alcohols, 0.5 ~ 1 part of catalyst, 5 ~ 10 parts of hexamethylenes, are passed through nitrogen protection, are stirred, then it is warming up to 170 ~
190 DEG C of heat preservations, are cooled to room temperature, and are evaporated under reduced pressure to get plasticizer additives.
The acid starting material are as follows: take carbic anhydride, 2- dimethyl succinic acid, hexahydrophthalic anhydride, trimellitic anhydride, 4- hydroxyl neighbour's benzene
Any one in dioctyl phthalate or it is any it is several by any mass ratio mix to get.
The raw polyol are as follows: take isooctanol, methyl propanediol, 1,4- butanediol, 1,2- propylene glycol, diethylene glycol (DEG), glycerine
In any one or it is any it is several by any mass ratio mix to get.
The catalyst are as follows: take active carbon 2 ~ 5:5 in mass ratio ~ 10 that column chromatography silica gel mixing is added, obtain mixture, take mixed
It is washed to close object, is kept the temperature in 110 ~ 120 DEG C, is cooled to room temperature, obtains cooled material, catalytic additive 3 ~ 5:5 ~ 10 in mass ratio is taken to add
Enter deionized water, obtain mixed liquor, take cooled material 2 ~ 6:20 in mass ratio ~ 25 that mixed liquor is added, stand, filter, takes suction filtration slag dry
It is dry to get catalyst.
The catalytic additive are as follows: take p-methyl benzenesulfonic acid 2 ~ 5:1 in mass ratio ~ 3 be added boron trifluoride mixing to get.
The resistance to migration additive the preparation method comprises the following steps: cyanogen is added in Copolymerization activity object 2 ~ 5:5 in mass ratio ~ 9:70 ~ 80
Acid esters activating agent, n,N-Dimethylformamide, are passed through nitrogen protection, are stirred, and obtain stirring mixture, take stirring mixture by
1,4-butanediol, dibutyltin dilaurate is added in 80 ~ 100:2 of mass ratio ~ 5:1 ~ 3, is warming up to 100 ~ 110 DEG C of heat preservations, cold
But to 50 ~ 60 DEG C, cooled material is obtained, takes cooled material 10 ~ 20:3 in mass ratio ~ 7 that dehydrated alcohol is added, is stood, rotary evaporation, is collected
Rotary evaporation residue is to get the additive of resistance to migration.
The Copolymerization activity object the preparation method comprises the following steps:
(1) according to the mass fraction, 3 ~ 9 parts of polypropylene glycols, 5 ~ 15 parts of maleic anhydrides, 60 ~ 70 parts of toluene, 1 ~ 3 part of metatitanic acid four are taken
Butyl ester, 3 ~ 5 parts of hydroquinones, are passed through nitrogen protection, are stirred, vacuum distillation, obtain vacuum distillation object, take vacuum distillation object by
Toluene, thionyl chloride is added in 2 ~ 5:40 of mass ratio ~ 50:20 ~ 30, is passed through nitrogen protection, is stirred, must stir mixture a；
(2) it takes stirring mixture a 5 ~ 10:2 in mass ratio ~ 5 that poly glycol monomethyl ether is added, is passed through nitrogen protection, is stirred,
Mixture b must be stirred, takes stirring mixture b 2 ~ 5:10 in mass ratio ~ 20 that ether is added, stands, takes precipitating dry to get copolymerization
Active matter.
The cyanate activating agent are as follows: according to the mass fraction, take 3 ~ 9 parts of 1,6- hexamethylene diisocyanates, more than 2 ~ 5 parts
Polymethylene polyphenyl polyisocyanates, the mixing of 1 ~ 3 part of 2,4- toluene-2,4-diisocyanate to get.
The dispersing additive are as follows: take oil with hydrogenated soybean 3 ~ 6:1 in mass ratio ~ 3 be added castor oil mixing to get.
The preparation method includes the following steps: to take plasticiser additive 10 ~ 15:2 in mass ratio ~ 5:40 ~ 50 that chlorination is added
Paraffin -52, cyclohexanone mixing, are passed through nitrogen protection, are stirred, be cooled to room temperature, obtain cooled material a, take cooled material a by quality
Resistance to migration additive is added than 50 ~ 60:25 ~ 30:50 ~ 60, dispersing additive is stirred to get the plasticising of resistance to migration environment-friendly type
Agent.
The present invention is compared with other methods, and advantageous effects are:
(1) plasticiser additive prepared by the present invention is to introduce low mass molecule alcohol using acid starting material and raw polyol as raw material and have benzene
The acid of ring structure carries out esterification, and forms covalent bond by nucleophilic displacement of fluorine and connect the ester type compound with benzene ring structure
Compound is formed on to chlorinated paraffin chain, so that obtained plasticizer additives had not only had esters structure but also had similar plasticising matrix
The compound of resin structure, on the one hand being formed by environment-friendly type raw material has the preferable plasticizer additives of heat resistance, and tree is added
It is swollen after aliphatic radical body, using macromolecular structure and highly branched chain group, so that the diffusion of plasticizer is also improved, separately
On the one hand the compatibility performance of plasticizer and resin is increased with similar structure using plasticizer and resin matrix, so that
It is formed and is crosslinked with resin, enhance plasticization effect；
(2) active carbon is added in the present invention during preparing plasticizer additives and the catalyst of column chromatography silica gel load is urged
Change esterification, the characteristic using p-methyl benzenesulfonic acid as non-oxidative strong acid is catalyzed, and the by-product formed is few, catalytic effect
Height improves the environmental-protecting performance of plasticizer during the preparation process, increases conversion ratio, so that obtained plasticizer performance boost；
(3) it is that raw material is reacted that resistance to migration additive prepared by the present invention, which is with Copolymerization activity object, cyanate activating agent etc., is obtained
To the oligomer of polyurethanes, there is preferable compatibility with resin matrix, connected using hydrogen bond by plasticizer and resin base
Body is anchored, and is formed and is fixed in matrix dispersion to plasticizer, is reduced the migration of plasticizer ester group and is reduced the dirt of environment
Dye, while the polyester soft segment introduced using Copolymerization activity object, provide flexibility for resin matrix, preferable improvement resin matrix
Temperature sensitivity, weatherability are improved so that plasticizer is still able to maintain flexibility under severe conditions, while have it is suitable
Relative molecular mass, can meet the processing technology of resin well, can also assist being plasticized and improve yellowing resistance, so that resin
Preferable performance is kept after matrix plasticising；
(4) present invention is first effectively catalyzed and is reacted to the raw material of plasticiser additive with catalyst, is had
It is preferably plasticized and has with resin matrix the plasticiser additive of preferable compatibility, then through resistance to migration additive in resin matrix
Plasticizer, which carries out anchoring, to be prevented from migrating and polluting environment, while the weatherability of resin matrix is improved using the Copolymerization activity object introduced
It is finally dispersed additive increase plasticizer so that resin matrix keeps excellent properties after plasticising with yellowing resistance energy and is being plasticized
Mobility and greasy property in the process can form uniform dispersion in resin matrix, improve plasticizing efficiency.
Specific embodiment
Acid starting material are as follows: take carbic anhydride, 2- dimethyl succinic acid, hexahydrophthalic anhydride, trimellitic anhydride, 4- hydroxyl O-phthalic
Any one in acid or it is any it is several by any mass ratio mix to get.
Raw polyol are as follows: take isooctanol, methyl propanediol, 1,4- butanediol, 1,2- propylene glycol, diethylene glycol (DEG), appoint in glycerine
Anticipate one or any of several by any mass ratio mix to get.
Catalytic additive are as follows: take p-methyl benzenesulfonic acid 2 ~ 5:1 in mass ratio ~ 3 be added boron trifluoride mixing to get.
Catalyst are as follows: take active carbon 2 ~ 5:5 in mass ratio ~ 10 that column chromatography silica gel mixing is added, obtain mixture, take mixture
Washed through deionized water, in 110 ~ 120 DEG C of 1 ~ 3h of heat preservation, be cooled to room temperature, obtain cooled material, take catalytic additive in mass ratio 3 ~
Deionized water is added in 5:5 ~ 10, obtains mixed liquor, takes cooled material 2 ~ 6:20 in mass ratio ~ 25 that mixed liquor is added, and stands 24 ~ 36h, takes out
Filter takes and takes out filter residue and drying to get catalyst.
Plasticiser additive the preparation method comprises the following steps: according to the mass fraction, taking 20 ~ 30 parts of acid starting materials, 30 ~ 50 parts of raw polyols, 3
~ 8 parts of 2-Ethylhexyl Alcohols, 0.5 ~ 1 part of catalyst, 5 ~ 10 parts of hexamethylenes, are passed through nitrogen protection, and it is mixed to be warming up to 150 ~ 160 DEG C of stirrings
20 ~ 30min is closed, then is warming up to 170 ~ 190 DEG C of 3 ~ 5h of heat preservation, is cooled to room temperature, is evaporated under reduced pressure to get plasticizer additives.
Copolymerization activity object the preparation method comprises the following steps:
(1) according to the mass fraction, 3 ~ 9 parts of polypropylene glycols, 5 ~ 15 parts of maleic anhydrides, 60 ~ 70 parts of toluene, 1 ~ 3 part of metatitanic acid four are taken
Butyl ester, 3 ~ 5 parts of hydroquinones, are passed through nitrogen protection, are warming up to 80 ~ 90 DEG C and are stirred 4 ~ 6h, and vacuum distillation must be evaporated under reduced pressure
Object takes vacuum distillation object 2 ~ 5:40 in mass ratio ~ 50:20 ~ 30 that toluene, thionyl chloride is added, nitrogen protection is passed through, in 40 ~ 50
DEG C it is stirred 2 ~ 4h, mixture a must be stirred；
(2) it takes stirring mixture a 5 ~ 10:2 in mass ratio ~ 5 that poly glycol monomethyl ether is added, nitrogen protection is passed through, in 70 ~ 80 DEG C
It is stirred 5 ~ 8h, mixture b must be stirred, takes stirring mixture b 2 ~ 5:10 in mass ratio ~ 20 that ether is added, is stood in 0 ~ 4 DEG C
1 ~ 4h takes precipitating dry to get Copolymerization activity object.
Cyanate activating agent are as follows: according to the mass fraction, take 3 ~ 9 parts of 1,6- hexamethylene diisocyanates, methylene more than 2 ~ 5 parts
Quito polyphenyl polyisocyanate, the mixing of 1 ~ 3 part of 2,4- toluene-2,4-diisocyanate to get.
Resistance to migration additive the preparation method comprises the following steps: cyanate is added in Copolymerization activity object 2 ~ 5:5 in mass ratio ~ 9:70 ~ 80
Activating agent, n,N-Dimethylformamide, are passed through nitrogen protection, are stirred 60 ~ 90min in 70 ~ 80 DEG C, obtain stirring mixture,
It takes stirring mixture 80 ~ 100:2 in mass ratio ~ 5:1 ~ 3 that 1,4-butanediol, dibutyltin dilaurate is added, is warming up to 100
~ 110 DEG C of 1 ~ 3h of heat preservation, are cooled to 50 ~ 60 DEG C, obtain cooled material, take cooled material 10 ~ 20:3 in mass ratio ~ 7 that dehydrated alcohol is added,
20 ~ 30min is stood, rotary evaporation collects rotary evaporation residue to get the additive of resistance to migration.
Dispersing additive are as follows: take oil with hydrogenated soybean 3 ~ 6:1 in mass ratio ~ 3 be added castor oil mixing to get.
A kind of preparation method of resistance to migration environment-friendlyplasticizer plasticizer, includes the following steps: to take plasticiser additive in mass ratio
Chlorinated paraffin -52, cyclohexanone mixing is added in 10 ~ 15:2 ~ 5:40 ~ 50, is passed through nitrogen protection, is stirred 1 ~ 3h in 60 ~ 65 DEG C,
It is cooled to room temperature, obtains cooled material a, take cooled material a 50 ~ 60:25 in mass ratio ~ 30:50 ~ 60 that resistance to migration additive, dispersion is added
Additive is stirred 1 ~ 3h in 70 ~ 80 DEG C to get resistance to migration environment-friendlyplasticizer plasticizer.
Embodiment 1
Acid starting material are as follows: take carbic anhydride, 2- dimethyl succinic acid by any mass ratio mix to get.
Raw polyol are as follows: take isooctanol, methyl propanediol by any mass ratio mix to get.
Catalytic additive are as follows: take p-methyl benzenesulfonic acid 2:1 in mass ratio be added boron trifluoride mixing to get.
Catalyst are as follows: take active carbon 2:5 in mass ratio that column chromatography silica gel mixing is added, obtain mixture, take catalytic additive
Deionized water is added in 3:5 in mass ratio, obtains mixed liquor, takes cooled material 2:20 in mass ratio that mixed liquor is added, and stands for 24 hours, filters,
It takes and takes out filter residue and drying to get catalyst.
Plasticiser additive the preparation method comprises the following steps: according to the mass fraction, taking 20 parts of acid starting materials, 30 parts of raw polyols, 3 parts of 2- second
Base hexanol, 0.5 part of catalyst, 5 parts of hexamethylenes, are passed through nitrogen protection, are warming up to 150 DEG C and are stirred 20min, then are warming up to
170 DEG C of heat preservation 3h, are cooled to room temperature, and are evaporated under reduced pressure to get plasticizer additives.
Copolymerization activity object the preparation method comprises the following steps:
(1) according to the mass fraction, take 3 parts of polypropylene glycols, 5 parts of maleic anhydrides, 60 parts of toluene, 1 part of butyl titanate, 3 parts it is right
Benzenediol is passed through nitrogen protection, is warming up to 80 DEG C and is stirred 4h, vacuum distillation, obtain vacuum distillation object, take vacuum distillation object by
Toluene, thionyl chloride is added in mass ratio 2:40:20, is passed through nitrogen protection, is stirred 2h in 40 DEG C, must stir mixture a；
(2) it takes stirring mixture a 5:2 in mass ratio that poly glycol monomethyl ether is added, is passed through nitrogen protection, is stirred in 70 DEG C
5h must stir mixture b, take stirring mixture b 2:10 in mass ratio that ether is added and take precipitating drying, i.e., in 0 DEG C of standing 1h
Obtain Copolymerization activity object.
Cyanate activating agent are as follows: according to the mass fraction, take 3 parts of 1,6- hexamethylene diisocyanates, 2 parts of polymethylenes more
Polyphenyl polyisocyanate, the mixing of 1 part of 2,4- toluene-2,4-diisocyanate to get.
It is resistance to migration additive the preparation method comprises the following steps: by Copolymerization activity object 2:5:70 in mass ratio be added cyanate activating agent,
N,N-Dimethylformamide is passed through nitrogen protection, is stirred 60min in 70 DEG C, obtains stirring mixture, take stirring mixture by
1,4-butanediol, dibutyltin dilaurate is added in mass ratio 80:2:1, is warming up to 100 DEG C of heat preservation 1h, is cooled to 50 DEG C, obtains
Cooled material takes cooled material 10:3 in mass ratio that dehydrated alcohol is added, and stands 20min, and it is remaining to collect rotary evaporation for rotary evaporation
Object is to get the additive of resistance to migration.
Dispersing additive are as follows: take oil with hydrogenated soybean 3:1 in mass ratio be added castor oil mixing to get.
A kind of preparation method of resistance to migration environment-friendlyplasticizer plasticizer, includes the following steps: to take plasticiser additive in mass ratio
Chlorinated paraffin -52, cyclohexanone mixing is added in 10:2:40, is passed through nitrogen protection, is stirred 1h in 60 DEG C, is cooled to room temperature, obtains
Cooled material a takes cooled material a 50:25:50 in mass ratio that resistance to migration additive, dispersing additive is added, is stirred in 70 DEG C
1h is to get resistance to migration environment-friendlyplasticizer plasticizer.
Embodiment 2
Acid starting material are as follows: take hexahydrophthalic anhydride, trimellitic anhydride by any mass ratio mix to get.
Raw polyol are as follows: take 1,4-butanediol, 1,2-PD by any mass ratio mix to get.
Catalytic additive are as follows: take p-methyl benzenesulfonic acid 3:2 in mass ratio be added boron trifluoride mixing to get.
Catalyst are as follows: take active carbon 4:8 in mass ratio that column chromatography silica gel mixing is added, obtain mixture, take catalytic additive
Deionized water is added in 4:8 in mass ratio, obtains mixed liquor, takes cooled material 4:23 in mass ratio that mixed liquor is added, and stands 30h, filters,
It takes and takes out filter residue and drying to get catalyst.
Plasticiser additive the preparation method comprises the following steps: according to the mass fraction, taking 25 parts of acid starting materials, 40 parts of raw polyols, 5 parts of 2- second
Base hexanol, 0.7 part of catalyst, 8 parts of hexamethylenes, are passed through nitrogen protection, are warming up to 155 DEG C and are stirred 25min, then are warming up to
180 DEG C of heat preservation 4h, are cooled to room temperature, and are evaporated under reduced pressure to get plasticizer additives.
Copolymerization activity object the preparation method comprises the following steps:
(1) according to the mass fraction, take 6 parts of polypropylene glycols, 10 parts of maleic anhydrides, 65 parts of toluene, 2 parts of butyl titanates, 4 parts it is right
Benzenediol is passed through nitrogen protection, is warming up to 85 DEG C and is stirred 5h, vacuum distillation, obtain vacuum distillation object, take vacuum distillation object by
Toluene, thionyl chloride is added in mass ratio 4:45:25, is passed through nitrogen protection, is stirred 3h in 45 DEG C, must stir mixture a；
(2) it takes stirring mixture a 8:4 in mass ratio that poly glycol monomethyl ether is added, is passed through nitrogen protection, is stirred in 75 DEG C
7h must stir mixture b, take stirring mixture b 4:15 in mass ratio that ether is added and take precipitating drying, i.e., in 2 DEG C of standing 3h
Obtain Copolymerization activity object.
Cyanate activating agent are as follows: according to the mass fraction, take 6 parts of 1,6- hexamethylene diisocyanates, 4 parts of polymethylenes more
Polyphenyl polyisocyanate, the mixing of 2 parts of 2,4- toluene-2,4-diisocyanates to get.
It is resistance to migration additive the preparation method comprises the following steps: by Copolymerization activity object 3:7:75 in mass ratio be added cyanate activating agent,
N,N-Dimethylformamide is passed through nitrogen protection, is stirred 75min in 75 DEG C, obtains stirring mixture, take stirring mixture by
1,4-butanediol, dibutyltin dilaurate is added in mass ratio 90:4:2, is warming up to 105 DEG C of heat preservation 2h, is cooled to 55 DEG C, obtains
Cooled material takes cooled material 15:5 in mass ratio that dehydrated alcohol is added, and stands 25min, and it is remaining to collect rotary evaporation for rotary evaporation
Object is to get the additive of resistance to migration.
Dispersing additive are as follows: take oil with hydrogenated soybean 4:2 in mass ratio be added castor oil mixing to get.
A kind of preparation method of resistance to migration environment-friendlyplasticizer plasticizer, includes the following steps: to take plasticiser additive in mass ratio
Chlorinated paraffin -52, cyclohexanone mixing is added in 12:3:45, is passed through nitrogen protection, is stirred 2h in 62 DEG C, is cooled to room temperature, obtains
Cooled material a takes cooled material a 55:28:55 in mass ratio that resistance to migration additive, dispersing additive is added, is stirred in 75 DEG C
2h is to get resistance to migration environment-friendlyplasticizer plasticizer.
Embodiment 3
Acid starting material are as follows: take trimellitic anhydride, 4- hydroxyl phthalic by any mass ratio mix to get.
Raw polyol are as follows: take diethylene glycol (DEG), glycerine by any mass ratio mix to get.
Catalytic additive are as follows: take p-methyl benzenesulfonic acid 5:3 in mass ratio be added boron trifluoride mixing to get.
Catalyst are as follows: take active carbon 5:10 in mass ratio that column chromatography silica gel mixing is added, obtain mixture, take catalytic additive
Deionized water is added in 5:10 in mass ratio, obtains mixed liquor, takes cooled material 6:25 in mass ratio that mixed liquor is added, and stands 36h, takes out
Filter takes and takes out filter residue and drying to get catalyst.
Plasticiser additive the preparation method comprises the following steps: according to the mass fraction, taking 30 parts of acid starting materials, 50 parts of raw polyols, 8 parts of 2- second
Base hexanol, 1 part of catalyst, 10 parts of hexamethylenes, are passed through nitrogen protection, are warming up to 160 DEG C and are stirred 30min, then are warming up to 190
DEG C heat preservation 5h, be cooled to room temperature, be evaporated under reduced pressure to get plasticizer additives.
Copolymerization activity object the preparation method comprises the following steps:
(1) according to the mass fraction, take 9 parts of polypropylene glycols, 15 parts of maleic anhydrides, 70 parts of toluene, 3 parts of butyl titanates, 5 parts it is right
Benzenediol is passed through nitrogen protection, is warming up to 90 DEG C and is stirred 6h, vacuum distillation, obtain vacuum distillation object, take vacuum distillation object by
Toluene, thionyl chloride is added in mass ratio 5:50:30, is passed through nitrogen protection, is stirred 4h in 50 DEG C, must stir mixture a；
(2) it takes stirring mixture a 10:5 in mass ratio that poly glycol monomethyl ether is added, is passed through nitrogen protection, it is mixed in 80 DEG C of stirrings
8h is closed, mixture b must be stirred, takes stirring mixture b 5:20 in mass ratio that ether is added and takes precipitating drying in 4 DEG C of standing 4h,
Up to Copolymerization activity object.
Cyanate activating agent are as follows: according to the mass fraction, take 9 parts of 1,6- hexamethylene diisocyanates, 5 parts of polymethylenes more
Polyphenyl polyisocyanate, the mixing of 3 parts of 2,4- toluene-2,4-diisocyanates to get.
It is resistance to migration additive the preparation method comprises the following steps: by Copolymerization activity object 5:9:80 in mass ratio be added cyanate activating agent,
N,N-Dimethylformamide is passed through nitrogen protection, is stirred 90min in 80 DEG C, obtains stirring mixture, take stirring mixture by
1,4-butanediol, dibutyltin dilaurate is added in mass ratio 100:5:3, is warming up to 110 DEG C of heat preservation 3h, is cooled to 60 DEG C,
Cooled material is obtained, takes cooled material 20:7 in mass ratio that dehydrated alcohol is added, stands 30min, it is remaining to collect rotary evaporation for rotary evaporation
Object is to get the additive of resistance to migration.
Dispersing additive are as follows: take oil with hydrogenated soybean 6:3 in mass ratio be added castor oil mixing to get.
A kind of preparation method of resistance to migration environment-friendlyplasticizer plasticizer, includes the following steps: to take plasticiser additive in mass ratio
Chlorinated paraffin -52, cyclohexanone mixing is added in 15:5:50, is passed through nitrogen protection, is stirred 3h in 65 DEG C, is cooled to room temperature, obtains
Cooled material a takes cooled material a 60:30:60 in mass ratio that resistance to migration additive, dispersing additive is added, is stirred in 80 DEG C
3h is to get resistance to migration environment-friendlyplasticizer plasticizer.
Comparative example 1: it is essentially identical with the preparation method of embodiment 1, it has only the difference is that lacking plasticiser additive.
Comparative example 2: it is essentially identical with the preparation method of embodiment 1, it has only the difference is that lacking the additive of resistance to migration.
Comparative example 3: it is essentially identical with the preparation method of embodiment 1, it has only the difference is that lacking dispersing additive.
Comparative example 4: the resistance to migration environment-friendlyplasticizer plasticizer of Shanghai City company production.
By resistance to migration environment-friendlyplasticizer plasticizer obtained by embodiment and comparative example according to GB1657-1981, GB/T1670-2008 into
Row test, test result are as shown in table 1:
Table 1:
In summary, the resulting resistance to migration environment-friendlyplasticizer plasticizer of the present invention is easy to migrate, environment-friendly type better performances, compared to commercially available
Product effect is more preferable, is worth promoting.
The foregoing is merely preferred modes of the invention, are not intended to limit the invention, all in spirit and original of the invention
Within then, any modification, equivalent replacement, improvement and so on be should all be included in the protection scope of the present invention.
Claims (10)
1. a kind of resistance to migration environment-friendlyplasticizer plasticizer, which is characterized in that add including plasticiser additive, resistance to migration additive, dispersion
Add agent；
The plasticizer additive the preparation method comprises the following steps: according to the mass fraction, taking 20 ~ 30 parts of acid starting materials, 30 ~ 50 parts of raw polyols, 3
~ 8 parts of 2-Ethylhexyl Alcohols, 0.5 ~ 1 part of catalyst, 5 ~ 10 parts of hexamethylenes, are passed through nitrogen protection, are stirred, then it is warming up to 170 ~
190 DEG C of heat preservations, are cooled to room temperature, and are evaporated under reduced pressure to get plasticizer additives.
2. resistance to migration environment-friendlyplasticizer plasticizer according to claim 1, which is characterized in that the acid starting material are as follows: take nadik
Acid anhydrides, 2- dimethyl succinic acid, hexahydrophthalic anhydride, trimellitic anhydride, any one in 4- hydroxyl phthalic any several are pressed
Any mass ratio mixing to get.
3. resistance to migration environment-friendlyplasticizer plasticizer according to claim 1, which is characterized in that the raw polyol are as follows: take isooctanol,
Methyl propanediol, 1,4- butanediol, 1,2- propylene glycol, diethylene glycol (DEG), any one in glycerine any several press any quality
Than mix to get.
4. resistance to migration environment-friendlyplasticizer plasticizer according to claim 1, which is characterized in that the catalyst are as follows: take active carbon
Column chromatography silica gel mixing is added in 2 ~ 5:5 in mass ratio ~ 10, obtains mixture, takes mixture washed, keeps the temperature in 110 ~ 120 DEG C, cold
But to room temperature, cooled material is obtained, takes catalytic additive 3 ~ 5:5 in mass ratio ~ 10 that deionized water is added, obtains mixed liquor, take cooled material
Mixed liquor is added in 2 ~ 6:20 in mass ratio ~ 25, stands, and filters, and takes and takes out filter residue and drying to get catalyst.
5. resistance to migration environment-friendlyplasticizer plasticizer according to claim 4, which is characterized in that the catalytic additive are as follows: take pair
Toluenesulfonic acid 2 ~ 5:1 in mass ratio ~ 3 be added boron trifluoride mixing to get.
6. resistance to migration environment-friendlyplasticizer plasticizer according to claim 1, which is characterized in that the preparation of the resistance to migration additive
Method are as follows: cyanate activating agent, n,N-Dimethylformamide is added in Copolymerization activity object 2 ~ 5:5 in mass ratio ~ 9:70 ~ 80, is led to
Enter nitrogen protection, be stirred, obtain stirring mixture, takes stirring mixture 80 ~ 100:2 in mass ratio ~ 5:1 ~ 3 that Isosorbide-5-Nitrae-fourth is added
Glycol, dibutyltin dilaurate are warming up to 100 ~ 110 DEG C of heat preservations, are cooled to 50 ~ 60 DEG C, obtain cooled material, take cooled material by
Dehydrated alcohol is added in 10 ~ 20:3 of mass ratio ~ 7, stands, rotary evaporation, collects rotary evaporation residue and adds to get resistance to migration
Agent.
7. resistance to migration environment-friendlyplasticizer plasticizer according to claim 6, which is characterized in that the preparation side of the Copolymerization activity object
Method are as follows:
(1) according to the mass fraction, 3 ~ 9 parts of polypropylene glycols, 5 ~ 15 parts of maleic anhydrides, 60 ~ 70 parts of toluene, 1 ~ 3 part of metatitanic acid four are taken
Butyl ester, 3 ~ 5 parts of hydroquinones, are passed through nitrogen protection, are stirred, vacuum distillation, obtain vacuum distillation object, take vacuum distillation object by
Toluene, thionyl chloride is added in 2 ~ 5:40 of mass ratio ~ 50:20 ~ 30, is passed through nitrogen protection, is stirred, must stir mixture a；
(2) it takes stirring mixture a 5 ~ 10:2 in mass ratio ~ 5 that poly glycol monomethyl ether is added, is passed through nitrogen protection, is stirred,
Mixture b must be stirred, takes stirring mixture b 2 ~ 5:10 in mass ratio ~ 20 that ether is added, stands, takes precipitating dry to get copolymerization
Active matter.
8. resistance to migration environment-friendlyplasticizer plasticizer according to claim 6, which is characterized in that the cyanate activating agent are as follows: press
Mass fraction meter takes 3 ~ 9 parts of 1,6- hexamethylene diisocyanates, 2 ~ 5 parts of poly methylene poly phenyl poly isocyanates, 1 ~ 3 part
2,4- toluene-2,4-diisocyanates mixing to get.
9. resistance to migration environment-friendlyplasticizer plasticizer according to claim 1, which is characterized in that the dispersing additive are as follows: take hydrogen
Change soybean oil 3 ~ 6:1 in mass ratio ~ 3 be added castor oil mixing to get.
10. a kind of preparation method of the resistance to migration environment-friendlyplasticizer plasticizer as described in claim 1 ~ 9 any one, feature exist
In the preparation method includes the following steps: to take plasticiser additive 10 ~ 15:2 in mass ratio ~ 5:40 ~ 50 that chlorinated paraffin-is added
52, cyclohexanone mix, be passed through nitrogen protection, be stirred, be cooled to room temperature, obtain cooled material a, take cooled material a in mass ratio 50 ~
Resistance to migration additive is added in 60:25 ~ 30:50 ~ 60, dispersing additive is stirred to get resistance to migration environment-friendlyplasticizer plasticizer.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201910125189.XA CN109867930A (en) | 2019-02-20 | 2019-02-20 | Resistance to migration environment-friendlyplasticizer plasticizer of one kind and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201910125189.XA CN109867930A (en) | 2019-02-20 | 2019-02-20 | Resistance to migration environment-friendlyplasticizer plasticizer of one kind and preparation method thereof |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN109867930A true CN109867930A (en) | 2019-06-11 |
Family
ID=66918980
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201910125189.XA Pending CN109867930A (en) | 2019-02-20 | 2019-02-20 | Resistance to migration environment-friendlyplasticizer plasticizer of one kind and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN109867930A (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN116082769A (en) * | 2023-03-22 | 2023-05-09 | 甘肃金川恒信高分子科技有限公司 | Environment-friendly polyvinyl chloride composite material and preparation method thereof |
| CN118005900A (en) * | 2024-04-08 | 2024-05-10 | 潍坊恒彩数码影像材料有限公司 | Plasticizer for industrial flaw detection film and preparation method thereof |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101775125A (en) * | 2010-02-04 | 2010-07-14 | 江南大学 | Non-aromatic nucleus structure poly-hexahydrobenzene phthalic anhydride dihydric alcohol ester plasticizer and preparation method thereof |
| CN103804669A (en) * | 2014-02-28 | 2014-05-21 | 江南大学 | Method for preparing caster oil-based polyester serving as PVC (Polyvinyl Chloride) plasticizer |
| US20180072867A1 (en) * | 2015-07-24 | 2018-03-15 | Lg Chem, Ltd. | Plasticizer composition, resin composition, and method of preparing the same |
| CN108410092A (en) * | 2018-04-10 | 2018-08-17 | 朱文杰 | A kind of preparation method of polyvinyl-chloride use plasticizer |
-
2019
- 2019-02-20 CN CN201910125189.XA patent/CN109867930A/en active Pending
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101775125A (en) * | 2010-02-04 | 2010-07-14 | 江南大学 | Non-aromatic nucleus structure poly-hexahydrobenzene phthalic anhydride dihydric alcohol ester plasticizer and preparation method thereof |
| CN103804669A (en) * | 2014-02-28 | 2014-05-21 | 江南大学 | Method for preparing caster oil-based polyester serving as PVC (Polyvinyl Chloride) plasticizer |
| US20180072867A1 (en) * | 2015-07-24 | 2018-03-15 | Lg Chem, Ltd. | Plasticizer composition, resin composition, and method of preparing the same |
| CN108410092A (en) * | 2018-04-10 | 2018-08-17 | 朱文杰 | A kind of preparation method of polyvinyl-chloride use plasticizer |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN116082769A (en) * | 2023-03-22 | 2023-05-09 | 甘肃金川恒信高分子科技有限公司 | Environment-friendly polyvinyl chloride composite material and preparation method thereof |
| CN116082769B (en) * | 2023-03-22 | 2023-06-27 | 甘肃金川恒信高分子科技有限公司 | Environment-friendly polyvinyl chloride composite material and preparation method thereof |
| CN118005900A (en) * | 2024-04-08 | 2024-05-10 | 潍坊恒彩数码影像材料有限公司 | Plasticizer for industrial flaw detection film and preparation method thereof |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| EP2984076B1 (en) | 2,5-tetrahydrofurane-esters and -ethers as plasticizers | |
| Chen et al. | Thermal behavior of epoxidized cardanol diethyl phosphate as novel renewable plasticizer for poly (vinyl chloride) | |
| KR102147417B1 (en) | Plasticizer and resin composition comprising the same | |
| CN103131150B (en) | Polypropylene/polylactic acid/starch composite material and preparation method thereof | |
| CN109867930A (en) | Resistance to migration environment-friendlyplasticizer plasticizer of one kind and preparation method thereof | |
| EP2181150B1 (en) | Low volatile organic content viscosity reducer | |
| CN108752803B (en) | Preparation method and application of adipic acid series environment-friendly polyester plasticizer with different and controllable molecular weights | |
| EP2817365B1 (en) | Succinic acid alkyl ester mixtures as softener | |
| CN113402891A (en) | Migration-resistant micro-crosslinked structure environment-friendly plasticizer and preparation method thereof | |
| CN103146095A (en) | Plasticized pvc compositions | |
| CN111574754A (en) | Basic formula of full-biodegradable button | |
| CN107778475A (en) | Nontoxic plasticiser of PTMEG classes and preparation method thereof | |
| EP3491053A1 (en) | Plasticizer composition | |
| CN105176363A (en) | Waterborne polyurethane wood primer resin and preparation method thereof | |
| CN113088543A (en) | Environment-friendly hyperbranched polyester plasticizer and preparation method thereof | |
| CN117887401A (en) | High-toughness corrosion-resistant polyurethane hot melt adhesive and preparation method thereof | |
| KR101437040B1 (en) | METHOD OF PRODUCITON FOR 1,3-PROPANDIOL BY ADDING osmoprotective substance AND MEDIUM FOR PRODUCITON OF 1,3-PROPANDIOL | |
| EP2890671B1 (en) | Plasticizers based on mixed esters of succinate | |
| EP3747860B1 (en) | Novel cyclohexanone based plasticisers | |
| CN105176364A (en) | Cationic polyurethane resin for waterborne wood primers and preparation method thereof | |
| EP3530690A1 (en) | Plasticizer composition comprising cyclohexane 1,4-diester-based compound, and resin composition comprising same | |
| EP2867287B1 (en) | Mixtures containing trimellitic acid esters and polyether polyol esters as plasticisers, use for the manufacture of polymer compounds, and pvc materials containing same | |
| CN108409574A (en) | A kind of citrate and its preparation method and application | |
| CN102666699A (en) | Plasticized polymeric compositions | |
| CN113105377A (en) | Preparation method of plasticizer and application of plasticizer in plastic product |
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 | ||
| WD01 | Invention patent application deemed withdrawn after publication |
Application publication date: 20190611 |
|
| WD01 | Invention patent application deemed withdrawn after publication |