CN107200865A - Containing multiple rigid ring structure plasticizer and preparation method and applications - Google Patents
Containing multiple rigid ring structure plasticizer and preparation method and applications Download PDFInfo
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- CN107200865A CN107200865A CN201710525374.9A CN201710525374A CN107200865A CN 107200865 A CN107200865 A CN 107200865A CN 201710525374 A CN201710525374 A CN 201710525374A CN 107200865 A CN107200865 A CN 107200865A
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- plasticizer
- ring structure
- rigid ring
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- 239000004014 plasticizer Substances 0.000 title claims abstract description 81
- 238000002360 preparation method Methods 0.000 title claims abstract description 16
- 239000004800 polyvinyl chloride Substances 0.000 claims abstract description 31
- 229920000915 polyvinyl chloride Polymers 0.000 claims abstract description 30
- QIGBRXMKCJKVMJ-UHFFFAOYSA-N Hydroquinone Chemical compound OC1=CC=C(O)C=C1 QIGBRXMKCJKVMJ-UHFFFAOYSA-N 0.000 claims abstract description 24
- 239000012043 crude product Substances 0.000 claims abstract description 23
- 238000005886 esterification reaction Methods 0.000 claims abstract description 11
- ILHIHKRJJMKBEE-UHFFFAOYSA-N hydroperoxyethane Chemical compound CCOO ILHIHKRJJMKBEE-UHFFFAOYSA-N 0.000 claims abstract description 10
- 230000032050 esterification Effects 0.000 claims abstract description 9
- PTPIRFSXRFIROJ-UHFFFAOYSA-N 2-(3-hydroxyphenoxy)ethane-1,1-diol Chemical compound OC(O)COC1=CC=CC(O)=C1 PTPIRFSXRFIROJ-UHFFFAOYSA-N 0.000 claims abstract description 8
- 239000000126 substance Substances 0.000 claims abstract description 8
- 239000003054 catalyst Substances 0.000 claims abstract description 7
- 230000003197 catalytic effect Effects 0.000 claims abstract description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 15
- WPYMKLBDIGXBTP-UHFFFAOYSA-N benzoic acid Chemical compound OC(=O)C1=CC=CC=C1 WPYMKLBDIGXBTP-UHFFFAOYSA-N 0.000 claims description 12
- -1 cyclopenta Chemical group 0.000 claims description 11
- 238000006243 chemical reaction Methods 0.000 claims description 7
- 239000005711 Benzoic acid Substances 0.000 claims description 6
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 6
- 235000010233 benzoic acid Nutrition 0.000 claims description 6
- 238000001035 drying Methods 0.000 claims description 6
- 239000000843 powder Substances 0.000 claims description 6
- 238000005406 washing Methods 0.000 claims description 6
- HNNQYHFROJDYHQ-UHFFFAOYSA-N 3-(4-ethylcyclohexyl)propanoic acid 3-(3-ethylcyclopentyl)propanoic acid Chemical compound CCC1CCC(CCC(O)=O)C1.CCC1CCC(CCC(O)=O)CC1 HNNQYHFROJDYHQ-UHFFFAOYSA-N 0.000 claims description 5
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 5
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 4
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 4
- JBDSSBMEKXHSJF-UHFFFAOYSA-N cyclopentanecarboxylic acid Chemical compound OC(=O)C1CCCC1 JBDSSBMEKXHSJF-UHFFFAOYSA-N 0.000 claims description 4
- 239000003960 organic solvent Substances 0.000 claims description 4
- 239000003381 stabilizer Substances 0.000 claims description 4
- ZRXHQNQYIKVKNQ-UHFFFAOYSA-N 2-ethylhexanoic acid;zinc Chemical compound [Zn].CCCCC(CC)C(O)=O ZRXHQNQYIKVKNQ-UHFFFAOYSA-N 0.000 claims description 3
- 239000000203 mixture Substances 0.000 claims description 3
- VXUYXOFXAQZZMF-UHFFFAOYSA-N titanium(IV) isopropoxide Chemical group CC(C)O[Ti](OC(C)C)(OC(C)C)OC(C)C VXUYXOFXAQZZMF-UHFFFAOYSA-N 0.000 claims description 3
- SMNDYUVBFMFKNZ-UHFFFAOYSA-N 2-furoic acid Chemical class OC(=O)C1=CC=CO1 SMNDYUVBFMFKNZ-UHFFFAOYSA-N 0.000 claims description 2
- 239000004135 Bone phosphate Substances 0.000 claims description 2
- 239000002253 acid Substances 0.000 claims description 2
- MRYMYQPDGZIGDM-UHFFFAOYSA-L copper;4-methylbenzenesulfonate Chemical compound [Cu+2].CC1=CC=C(S([O-])(=O)=O)C=C1.CC1=CC=C(S([O-])(=O)=O)C=C1 MRYMYQPDGZIGDM-UHFFFAOYSA-L 0.000 claims description 2
- 125000000113 cyclohexyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])C1([H])[H] 0.000 claims description 2
- 238000004821 distillation Methods 0.000 claims description 2
- 125000002541 furyl group Chemical group 0.000 claims description 2
- PIJPYDMVFNTHIP-UHFFFAOYSA-L lead sulfate Chemical compound [PbH4+2].[O-]S([O-])(=O)=O PIJPYDMVFNTHIP-UHFFFAOYSA-L 0.000 claims description 2
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 2
- 230000035484 reaction time Effects 0.000 claims description 2
- JXHZRQHZVYDRGX-UHFFFAOYSA-M sodium;hydrogen sulfate;hydrate Chemical compound [OH-].[Na+].OS(O)(=O)=O JXHZRQHZVYDRGX-UHFFFAOYSA-M 0.000 claims description 2
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 2
- 229910052787 antimony Inorganic materials 0.000 claims 1
- WATWJIUSRGPENY-UHFFFAOYSA-N antimony atom Chemical compound [Sb] WATWJIUSRGPENY-UHFFFAOYSA-N 0.000 claims 1
- MJEMIOXXNCZZFK-UHFFFAOYSA-N ethylone Chemical compound CCNC(C)C(=O)C1=CC=C2OCOC2=C1 MJEMIOXXNCZZFK-UHFFFAOYSA-N 0.000 claims 1
- 230000003647 oxidation Effects 0.000 claims 1
- 238000007254 oxidation reaction Methods 0.000 claims 1
- VWDWKYIASSYTQR-UHFFFAOYSA-N sodium nitrate Chemical compound [Na+].[O-][N+]([O-])=O VWDWKYIASSYTQR-UHFFFAOYSA-N 0.000 claims 1
- 239000000047 product Substances 0.000 abstract description 28
- 238000013508 migration Methods 0.000 abstract description 12
- 230000005012 migration Effects 0.000 abstract description 12
- 238000000746 purification Methods 0.000 abstract description 5
- 238000002329 infrared spectrum Methods 0.000 abstract description 4
- 239000011347 resin Substances 0.000 abstract description 3
- 229920005989 resin Polymers 0.000 abstract description 3
- 238000012512 characterization method Methods 0.000 abstract description 2
- 238000001819 mass spectrum Methods 0.000 abstract description 2
- 239000004597 plastic additive Substances 0.000 abstract description 2
- 238000000425 proton nuclear magnetic resonance spectrum Methods 0.000 abstract 1
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 16
- 238000012360 testing method Methods 0.000 description 15
- 238000004088 simulation Methods 0.000 description 14
- 210000003296 saliva Anatomy 0.000 description 13
- 210000004243 sweat Anatomy 0.000 description 13
- 239000012153 distilled water Substances 0.000 description 12
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonia chloride Chemical compound [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 description 8
- WCUXLLCKKVVCTQ-UHFFFAOYSA-M Potassium chloride Chemical compound [Cl-].[K+] WCUXLLCKKVVCTQ-UHFFFAOYSA-M 0.000 description 8
- 238000001914 filtration Methods 0.000 description 8
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 description 8
- 239000011780 sodium chloride Substances 0.000 description 8
- MQIUGAXCHLFZKX-UHFFFAOYSA-N Di-n-octyl phthalate Natural products CCCCCCCCOC(=O)C1=CC=CC=C1C(=O)OCCCCCCCC MQIUGAXCHLFZKX-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
- 125000000217 alkyl group Chemical group 0.000 description 5
- 229910000410 antimony oxide Inorganic materials 0.000 description 5
- 238000000034 method Methods 0.000 description 5
- 230000037230 mobility Effects 0.000 description 5
- VTRUBDSFZJNXHI-UHFFFAOYSA-N oxoantimony Chemical compound [Sb]=O VTRUBDSFZJNXHI-UHFFFAOYSA-N 0.000 description 5
- NSJFQBFLPMIGFZ-UHFFFAOYSA-N 2-hydroxypropanoic acid;urea Chemical compound NC(N)=O.CC(O)C(O)=O NSJFQBFLPMIGFZ-UHFFFAOYSA-N 0.000 description 4
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical compound [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 description 4
- 235000019270 ammonium chloride Nutrition 0.000 description 4
- 238000005119 centrifugation Methods 0.000 description 4
- 150000002148 esters Chemical class 0.000 description 4
- 235000019441 ethanol Nutrition 0.000 description 4
- 238000010438 heat treatment Methods 0.000 description 4
- 229910000027 potassium carbonate Inorganic materials 0.000 description 4
- 239000001103 potassium chloride Substances 0.000 description 4
- 235000011164 potassium chloride Nutrition 0.000 description 4
- 239000002994 raw material Substances 0.000 description 4
- 239000000376 reactant Substances 0.000 description 4
- 238000000926 separation method Methods 0.000 description 4
- 238000002791 soaking Methods 0.000 description 4
- 230000009182 swimming Effects 0.000 description 4
- 238000010792 warming Methods 0.000 description 4
- 238000005303 weighing Methods 0.000 description 4
- OBETXYAYXDNJHR-SSDOTTSWSA-M (2r)-2-ethylhexanoate Chemical compound CCCC[C@@H](CC)C([O-])=O OBETXYAYXDNJHR-SSDOTTSWSA-M 0.000 description 3
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 3
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 3
- OBETXYAYXDNJHR-UHFFFAOYSA-N alpha-ethylcaproic acid Natural products CCCCC(CC)C(O)=O OBETXYAYXDNJHR-UHFFFAOYSA-N 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 239000001257 hydrogen Substances 0.000 description 3
- 229910052739 hydrogen Inorganic materials 0.000 description 3
- 229920000642 polymer Polymers 0.000 description 3
- 239000002904 solvent Substances 0.000 description 3
- 239000011701 zinc Substances 0.000 description 3
- 229910052725 zinc Inorganic materials 0.000 description 3
- 238000005160 1H NMR spectroscopy Methods 0.000 description 2
- BJEJEBOUUCXCRZ-UHFFFAOYSA-N 2-(2-hydroxyphenoxy)ethane-1,1-diol Chemical compound OC(COC=1C(=CC=CC=1)O)O BJEJEBOUUCXCRZ-UHFFFAOYSA-N 0.000 description 2
- 238000010521 absorption reaction Methods 0.000 description 2
- 238000011161 development 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
- 230000005611 electricity Effects 0.000 description 2
- 238000002290 gas chromatography-mass spectrometry Methods 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 238000005259 measurement Methods 0.000 description 2
- IOLCXVTUBQKXJR-UHFFFAOYSA-M potassium bromide Chemical compound [K+].[Br-] IOLCXVTUBQKXJR-UHFFFAOYSA-M 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 238000001228 spectrum Methods 0.000 description 2
- 150000005208 1,4-dihydroxybenzenes Chemical class 0.000 description 1
- LSNNMFCWUKXFEE-UHFFFAOYSA-M Bisulfite Chemical compound OS([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-M 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
- 230000006750 UV protection Effects 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- KKEYFWRCBNTPAC-UHFFFAOYSA-N benzene-dicarboxylic acid Natural products OC(=O)C1=CC=C(C(O)=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-N 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- HEDRZPFGACZZDS-MICDWDOJSA-N deuterated chloroform Substances [2H]C(Cl)(Cl)Cl HEDRZPFGACZZDS-MICDWDOJSA-N 0.000 description 1
- 235000014113 dietary fatty acids Nutrition 0.000 description 1
- 238000006073 displacement reaction Methods 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 229920001971 elastomer Polymers 0.000 description 1
- 239000000806 elastomer Substances 0.000 description 1
- 239000000194 fatty acid Substances 0.000 description 1
- 229930195729 fatty acid Natural products 0.000 description 1
- 230000009975 flexible effect Effects 0.000 description 1
- 235000013305 food Nutrition 0.000 description 1
- OFEVLLPPRKRSAN-UHFFFAOYSA-N formic acid;hexane Chemical compound OC=O.CCCCCC OFEVLLPPRKRSAN-UHFFFAOYSA-N 0.000 description 1
- 238000007306 functionalization reaction Methods 0.000 description 1
- 230000009477 glass transition Effects 0.000 description 1
- 230000036541 health Effects 0.000 description 1
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-M hydrogensulfate Chemical compound OS([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-M 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 239000002649 leather substitute Substances 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 229920002521 macromolecule Polymers 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 231100000956 nontoxicity Toxicity 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
- 229920003023 plastic Polymers 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 231100000175 potential carcinogenicity Toxicity 0.000 description 1
- 238000003825 pressing Methods 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- RLJWTAURUFQFJP-UHFFFAOYSA-N propan-2-ol;titanium Chemical group [Ti].CC(C)O.CC(C)O.CC(C)O.CC(C)O RLJWTAURUFQFJP-UHFFFAOYSA-N 0.000 description 1
- 230000004224 protection Effects 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 238000010183 spectrum analysis Methods 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- 230000009466 transformation Effects 0.000 description 1
Classifications
-
- 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
- C08K5/103—Esters; Ether-esters of monocarboxylic acids with polyalcohols
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C67/00—Preparation of carboxylic acid esters
- C07C67/08—Preparation of carboxylic acid esters by reacting carboxylic acids or symmetrical anhydrides with the hydroxy or O-metal group of organic compounds
-
- 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
- C08K2201/00—Specific properties of additives
- C08K2201/014—Additives containing two or more different additives of the same subgroup in C08K
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2201/00—Properties
- C08L2201/04—Antistatic
-
- 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)
- Compositions Of Macromolecular Compounds (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention discloses containing multiple rigid ring structure plasticizer and preparation method and applications, belong to plastic additive technical field.The preparation method is included a kind of and a kind of monoacid containing rigid ring structure in resorcinol dihydroxyethyl ether or hydroquinone two hydroxy ethyl ether, esterification is carried out under the catalytic action of catalyst and condition of high vacuum degree, prepare plasticizer crude product, again by the purification process in later stage, plasticizer pure substance is prepared, the plasticizer pure substance carries out structural characterization by proton nmr spectra, mass spectrum and infrared spectrum respectively.Prepared by the present invention is mainly used in polyvinyl chloride resin containing multiple rigid ring structure plasticizer, prepared by the present invention heat endurance and resistance to migration that plasticizer is not only effectively raised containing multiple rigid ring structure plasticizer, and the antistatic behaviour of PVC product is improved well, greatly expand the use scope of PVC product.
Description
Technical field
The present invention relates to plastic additive technical field, more particularly to containing multiple rigid ring structure plasticizer and preparation method
And its application.
Background technology
Plasticizer is a kind of to be added in plastics, resin or elastomer to improve their processability, plasticity, flexible
Property, draftability, but do not change the material for being plasticized material basic chemical property.It is mainly used in polyvinyl chloride (PVC) resin,
Consumption in PVC can account for more than the 98% of whole plasticizer consumption, therefore the development of plasticizer and PVC industrial expansions breath breath
It is related.Domestic conventional plasticizer kind mainly includes phthalate, terephthalic acid ester, alkyl sulfonic acid benzene now
Esters, fatty acid ester etc., its yield account for the 80% of plasticizer total amount.In recent years, with science and technology develop rapidly and
More expectations of the people to Green Chemistry, the performance to plasticizer proposes higher and higher requirement, therefore Development and Production is more
Plasticizer with high-performance, functionalization, nontoxicity, customizations turns into the emphasis of current plasticizer research field.
Conventional plasticizers such as dioctyl phthalate (DOP), diisononyl phthalate (DINP) etc. are to make at present
With most commonly used class plasticizer, because it has long alkyl chain structure, make amorphous region volume increase, increase polymerization owner
Chain moving machine meeting, so as to significantly reduce the glass transition temperature of polymer, imparts the more preferable processing characteristics of product.Together
When, long alkyl chain structure has screen effect and lubricity to polymer macromolecule, can be greatly enhanced polymer compliance,
Ultraviolet resistance and cold resistance.But with deepening continuously for research, this class plasticizer shortcoming be also gradually exposed, it is longer
Alkyl chain structure makes plasticizer volatility larger, and thermodynamic property is unstable, causes product intolerant to migration, after long-time use
Product surface easily softens, tacky or even rupture, substantially reduces the using effect of product.Resistance to migration is generally and anti-pollution simultaneously
Property related, the poor product of migration generally not anti-pollution, this can also reduce the using effect of product.
Application of the universal phthalic ester plasticizer in the industries such as medicine equipment, food, toy, artificial leather is got over
Come more extensive, in addition to itself there is potential carcinogenicity outside, and due to its long alkyl chain structure, in PVC product easily
Migrate and extracted out by solvent, not only influence properties of product, also directly threaten the health of the mankind.
The content of the invention
Existing plasticizer technology is due to causing easily migration using universal phthalic ester plasticizer, easily into quilt
In the solvent (such as water, alcohols) of extracting, influence user's is healthy.
In order to solve the above technical problems, the invention discloses the preparation method containing multiple rigid ring structure plasticizer.Using
The preparation method has obtained the plasticizer of the multiple rigid ring structures of introducing, not only effectively raise plasticizer heat endurance and
Resistance to migration, and the antistatic behaviour of PVC product is improved well, greatly expand the use scope of PVC product.
To achieve the above object, the invention provides containing multiple rigid ring structure plasticizer, molecular structural formula such as Formulas I or formula
Shown in II：
The one kind of group R in phenyl, cyclopenta, cyclohexyl, furyl in Formulas I or Formula II.
Technical scheme to better implement the present invention, the invention also discloses the system containing multiple rigid ring structure plasticizer
Preparation Method, comprises the following steps：
1) plasticizer crude product is prepared：By in resorcinol dihydroxyethyl ether or hydroquinone two hydroxy ethyl ether one kind with
A kind of monoacid containing rigid ring structure is placed in reaction vessel, carries out being esterified instead under the catalytic action of catalyst and low pressure
Should, plasticizer crude product is prepared, preferably absolute pressure is 100Pa or so, and plasticizer crude product is to contain part by-product
The plasticizer of thing, shown in the molecular formula Formulas I described above or Formula II of the plasticizer；
2) plasticizer crude product is purified：By the step 1) the plasticizer crude product for preparing distillation water washing, mistake
Filter at least three times, then recrystallized with organic solvent, is finally centrifuged, is filtered, drying prepares plasticizer, neat again
Net thing, the plasticizer pure substance is the product shown in molecular formula main Formulas I or Formula II described above.
Further, the step 1) in, the monoacid containing rigid ring structure is cyclopentane-carboxylic acid, benzoic acid, ring
One kind in hexane formic acid, 2- furancarboxylic acids.
Yet further, the step 1) in, the catalyst is tetraisopropyl titanate, copper p-toluenesulfonate, hydrogen sulfate
One kind in sodium, Sodium Bisulfate Monohydrate, antimony oxide, the consumption of the catalyst is the unitary acid substance containing rigid ring structure
Amount 1%~2%.
Further, the step 1) in, one in resorcinol dihydroxyethyl ether or hydroquinone two hydroxy ethyl ether
The mol ratio planted with the monoacid containing rigid ring structure is 1: 2.1~2.4.
Further, the step 1) in, esterification reaction temperature is controlled in 80 DEG C~130 DEG C, reaction time of esterification control
It is made as 3~4h.
Further, the step 2) in, the organic solvent is in absolute ethyl alcohol, ether, acetone, tetrahydrofuran
It is a kind of.
The application in polyvinyl chloride is prepared containing multiple rigid ring structure plasticizer prepared by the present invention, according to following components
Polyvinyl chloride is prepared, mass ratio is：Polyvinyl chloride powder: plasticizer: stabilizer=100: (30~50): (1~3) is mixed to get mixed
Compound, carries out banburying, polyvinyl chloride sample is made in last tabletting by banbury by the mixture of acquisition under conditions of 150 DEG C
Product, the stabilizer is one kind in 2 ethyl hexanoic acid zinc, thiol-butyl tin, lead sulfate tribasic.
Simultaneously in order to which the plasticizer product prepared to the present invention carries out structural characterization, nucleus magnetic hydrogen spectrum, mass spectrum have been carried out respectively
And examination of infrared spectrum, test the instrument used as follows：
What the present invention was provided contains multiple rigid ring structure plasticizer1H-NMR uses the cores of Bruker Avance DMX 400
Magnetic resonance device, TMS is used as internal standard, CDCl3Make solvent；
Infrared spectrum analysis uses FTIR-650 FTISs, and method of testing is to use pressing potassium bromide troche
Method, in 400-4000cm-1In the range of record sample skeletal vibration infrared absorption peak；
Mass spectral analysis uses the 7890A/5975C gas chromatography mass spectrometry chromatographs of Agilent companies of the U.S., and the μ L of sample size 1.0 enter
250 DEG C of temperature of sample mouthful, HP-5MS capillary chromatographic columns, column temperature initial temperature is 50 DEG C, and 240 DEG C, holding are risen to 10 DEG C/min
1min。
Beneficial effect：
1st, the plasticizer for preparing of the present invention introduces rigid ring structure, effectively raise plasticizer heat endurance and
Resistance to migration；
2nd, the plasticizer that the present invention is prepared can improve the antistatic behaviour of PVC product well, greatly expand PVC systems
The use scope of product；
3rd, preparation method of the invention is simple, and income is higher.
Brief description of the drawings
Fig. 1 is the nucleus magnetic hydrogen spectrum figure of hydroquinone two hydroxy ethyl ether-benzoic acid diester prepared by the embodiment of the present invention；
Fig. 2 is the mass spectrogram of the hydroquinone two hydroxy ethyl ether-benzoic acid diester prepared in Fig. 1；
Fig. 3 is the infrared spectrogram of resorcinol dihydroxyethyl ether-benzoic acid diester prepared by the embodiment of the present invention.
Embodiment
In order to preferably explain the present invention, below in conjunction with specific embodiment and accompanying drawing the present invention is furture elucidated it is main in
Hold, but present disclosure is not limited solely to following examples.
Embodiment 1：Plasticizer is prepared using hydroquinone two hydroxy ethyl ether and benzoic acid as raw material：
Esterification prepares crude product：4.396g benzoic acid, 3.033g pair are sequentially added in 50ml single-necked flasks
The antimony oxide of benzenediol dihydroxyethyl ether and 0.08g, be gradually warming up to 85 DEG C make reactant be completely dissolved after by circulation
Ability of swimming vavuum pump, which is vacuumized, makes pressure in single-necked flask keep 100Pa or so, and temperature control is 90 DEG C and reacts 3 hours, finally
Increase the temperature to 120 DEG C to react 1 hour, stop after heating, naturally cool to room temperature, obtain plasticizer crude product 6.919g.On
The chemical equation for stating reaction is as follows：
The Separation ＆ Purification of crude product：Will gained plasticizer crude product distilled water washing and filtering three times after reaction, then
Recrystallized with absolute ethyl alcohol, refined plasticizer product 5.841g, yield are obtained after eventually passing centrifugation, filtering, drying
For 78.62%.
In order to further verify benzenediol dihydroxyethyl ether-benzoic ether manufactured in the present embodiment, use1H-NMR and
GC-MS is characterized to product manufactured in the present embodiment, has respectively obtained Fig. 1 and Fig. 2, is understood with reference to Fig. 1, Fig. 1 hydroquinones
The displacement of the various hydrogen of dihydroxyethyl ether-benzoic acid diester and numbers of hydrogen atoms have all done corresponding mark, and embody respectively such as
Under：
Prepare PVC (polyvinyl chloride) tabletting：By following components consumption：100 parts of PVC powder, plasticising prepared by above-described embodiment 1
30 parts of agent, 1 part of 2 ethyl hexanoic acid zinc, it is 150 DEG C of progress banburyings, then tabletting that temperature is controlled in banbury.
Simulation prepares sweat：Sodium acid carbonate 4g, sodium chloride 0.5g, potassium carbonate 0.35g are weighed, is arrived with distilled water constant volume
1000ml, that is, obtain the simulated sweat that pH is 8.8.
Simulation prepares saliva：Sodium chloride 4.5g, potassium chloride 0.3g, ammonium chloride 0.4g, 90% lactic acid urea 0.2g are weighed,
With distilled water constant volume to 1000ml, that is, obtain the simulation saliva that pH is 3.04.
Take PVC tablettings to be respectively put into Simulated sweat and saliva, soak 30 minutes at room temperature, carry out resistance to migration survey
Examination, compares the size of mobility, test result is as shown in table 1 by weighing the tablet quality before and after soaking.Separately take PVC tablettings
Resistivity measurement is carried out, the method for testing of resistivity meets GB/T1410-1989 standards, and test result is as shown in table 2.
Embodiment 2：Plasticizer is prepared using resorcinol dihydroxyethyl ether and benzoic acid as raw material：
Esterification prepares crude product：Sequentially added in 50ml single-necked flasks between 4.396g benzoic acid, 3.033g
The antimony oxide of benzenediol dihydroxyethyl ether and 0.08g, be gradually warming up to 85 DEG C make reactant be completely dissolved after by circulation
Ability of swimming vavuum pump, which is vacuumized, makes the pressure in single-necked flask keep 100Pa or so, and temperature control is 90 DEG C and reacted 3 hours.Finally
Increase the temperature to 120 DEG C to react 1 hour, stop heating and allow it to naturally cool to room temperature, obtain plasticizer crude product 7.095g
The Separation ＆ Purification of crude product：Will products therefrom distilled water washing and filtering three times after reaction, then use anhydrous second
Alcohol is recrystallized, and obtains refined plasticizer product 5.677g after eventually passing centrifugation, filtering, drying, yield is
76.42%.
In order to further verify resorcinol dihydroxyethyl ether-benzoic acid diester manufactured in the present embodiment, using infrared
Spectrum is characterized to product manufactured in the present embodiment, has obtained Fig. 3.Ester carbonyl group is in 1714cm as shown in Figure 3-1Place absorbs, ester
C-O stretching vibrations in 1162cm-1Place absorbs, while in 3467cm-1Place is without there is obvious hydroxyl absorption peak, so can
Expected esterification is there occurs to say, and generates expected product.
Prepare PVC tablettings：By following components consumption：100 parts of PVC powder, 30 parts of the implementation case plasticizer, 2 ethyl hexanoic acid
1 part of zinc, 150 DEG C of banburyings, tabletting.
Simulation prepares sweat：Weigh and take sodium acid carbonate 4g, sodium chloride 0.5g, potassium carbonate 0.35g are arrived with distilled water constant volume
1000ml, that is, obtain the simulated sweat that pH is 8.8.
Simulation prepares saliva：Sodium chloride 4.5g, potassium chloride 0.3g, ammonium chloride 0.4g, 90% lactic acid urea 0.2g are weighed,
With distilled water constant volume to 1000ml, that is, obtain the simulation saliva that pH is 3.04.
Take the PVC tablettings prepared to be respectively put into Simulated sweat and saliva, soak 30 minutes at room temperature, carry out resistance to
Migration is tested, and compares the size of mobility by weighing the tablet quality before and after soaking, test result is as shown in table 1.Separately
Pressure piece carries out resistivity measurement, and the method for testing of resistivity meets GB/T1410-1989 standards, and test result is as shown in table 2.
Embodiment 3：Plasticizer is prepared using hydroquinone two hydroxy ethyl ether and naphthenic acid as raw material：
Esterification prepares crude product：4.614g naphthenic acid, 3.033g are sequentially added in 50ml single-necked flasks
Hydroquinone two hydroxy ethyl ether and 0.1g antimony oxide, be gradually warming up to 85 DEG C make reactant be completely dissolved after by following
Ring ability of swimming vavuum pump, which is vacuumized, makes the pressure in single-necked flask keep 100Pa or so, and temperature control is 90 DEG C and reacted 3 hours.Most
After increase the temperature to 120 DEG C react 1 hour, stop heating allowing it to naturally cool to room temperature, obtain plasticizer crude product 7.102g.
The Separation ＆ Purification of crude product：Will products therefrom distilled water washing and filtering three times after reaction, then use anhydrous second
Alcohol is recrystallized, and obtains refined plasticizer product 5.904g after eventually passing centrifugation, filtering, drying, yield is
77.21%.
Prepare PVC tablettings：By following components consumption：100 parts of PVC powder, 30 parts of the implementation case plasticizer, 2 ethyl hexanoic acid
1 part of zinc, 150 DEG C of banburyings, tabletting.
Simulation prepares sweat：Weigh and take sodium acid carbonate 4g, sodium chloride 0.5g, potassium carbonate 0.35g are arrived with distilled water constant volume
1000ml, that is, obtain the simulated sweat that pH is 8.8.
Simulation prepares saliva：Sodium chloride 4.5g, potassium chloride 0.3g, ammonium chloride 0.4g, 90% lactic acid urea 0.2g are weighed,
With distilled water constant volume to 1000ml, that is, obtain the simulation saliva that pH is 3.04.
Pressure piece is respectively put into Simulated sweat and saliva, is soaked 30 minutes at room temperature, carries out resistance to migration test,
Compare the size of mobility by weighing the tablet quality before and after soaking, test result is as shown in table 1.Another pressure piece carries out electricity
Resistance rate is tested, and the method for testing of resistivity meets GB/T1410-1989 standards, and test result is as shown in table 2.
Embodiment 4：Plasticizer is prepared using resorcinol dihydroxyethyl ether and naphthenic acid as raw material：
Esterification prepares crude product：4.614g naphthenic acid, 3.033g are sequentially added in 50ml single-necked flasks
Hydroquinone two hydroxy ethyl ether and 0.1g antimony oxide, be gradually warming up to 85 DEG C make reactant be completely dissolved after by following
Ring ability of swimming vavuum pump, which is vacuumized, makes the pressure in single-necked flask keep 100Pa or so, and temperature control is 90 DEG C and reacted 3 hours.Most
After increase the temperature to 120 DEG C react 1 hour, stop heating allowing it to naturally cool to room temperature, obtain plasticizer crude product 6.985g.
The Separation ＆ Purification of crude product：Will products therefrom distilled water washing and filtering three times after reaction, then use anhydrous second
Alcohol is recrystallized, and obtains refined plasticizer product 6.005g after eventually passing centrifugation, filtering, drying, yield is
78.53%.
Prepare PVC tablettings：By following components consumption：100 parts of PVC powder, 30 parts of the implementation case plasticizer, 2 ethyl hexanoic acid
1 part of zinc, 150 DEG C of banburyings, tabletting.
Simulation prepares sweat：Weigh and take sodium acid carbonate 4g, sodium chloride 0.5g, potassium carbonate 0.35g are arrived with distilled water constant volume
1000ml, that is, obtain the simulated sweat that pH is 8.8.
Simulation prepares saliva：Sodium chloride 4.5g, potassium chloride 0.3g, ammonium chloride 0.4g, 90% lactic acid urea 0.2g are weighed,
With distilled water constant volume to 1000ml, that is, obtain the simulation saliva that pH is 3.04.
Pressure piece is respectively put into Simulated sweat and saliva, is soaked 30 minutes at room temperature, carries out resistance to migration test,
Compare the size of mobility by weighing the tablet quality before and after soaking, test result is as shown in table 1.Another pressure piece carries out electricity
Resistance rate is tested, and the method for testing of resistivity meets GB/T1410-1989 standards, and test result is as shown in table 2.
Plasticizer prepared by the 1~embodiment of embodiment 4 of table 1 and the comparison of the resistance to mobilities of DOP
As can be seen from Table 1, increasing due to rigid ring structure, plasticizer prepared by the present invention is with respect to DOP to simulation sweat
Liquid and simulation saliva possess preferable resistance to migration.
The comparison of plasticizer prepared by the 1~embodiment of embodiment 4 of table 2 and DOP resistance
As can be seen from Table 2, the plasticizer that prepared by the present invention has relatively higher resistance compared to DOP, adds PVC systems
The electrical insulating property and antistatic behaviour of product.
Above example is only optimal citing, and is not the restriction to embodiments of the present invention.Except above-described embodiment
Outside, the present invention also has other embodiment.All use equivalent substitutions or the technical scheme of equivalent transformation formation, all fall within the present invention
It is required that protection domain in.
Claims (9)
1. one kind contains multiple rigid ring structure plasticizer, it is characterised in that：Molecular structural formula is as shown in Formulas I or Formula II：
Group R in Formulas I or Formula II is one kind in phenyl, cyclopenta, cyclohexyl, furyl.
2. a kind of preparation method for containing multiple rigid ring structure plasticizer as claimed in claim 1, it is characterised in that：Including such as
Lower step：
1) plasticizer crude product is prepared：By one kind in resorcinol dihydroxyethyl ether or hydroquinone two hydroxy ethyl ether and one kind
Monoacid containing rigid ring structure is placed in reaction vessel, under the catalytic action of catalyst and 50~200pa absolute pressure
Esterification is carried out, plasticizer crude product is prepared；
2) plasticizer crude product is purified：By the step 1) the plasticizer crude product for preparing distillation water washing, filter extremely
It is few three times, then recrystallized with organic solvent, finally centrifuged, filtered again, drying prepares plasticizer pure substance.
3. the preparation method according to claim 2 containing multiple rigid ring structure plasticizer, it is characterised in that：The step
1) in, the monoacid containing rigid ring structure is one in cyclopentane-carboxylic acid, benzoic acid, naphthenic acid, 2- furancarboxylic acids
Kind.
4. the preparation method containing multiple rigid ring structure plasticizer according to Claims 2 or 3, it is characterised in that：It is described
Step 1) in, the catalyst is tetraisopropyl titanate, copper p-toluenesulfonate, niter cake, Sodium Bisulfate Monohydrate, three oxidations two
One kind in antimony, the consumption of the catalyst is the 1%~2% of the amount of the unitary acid substance containing rigid ring structure.
5. the preparation method containing multiple rigid ring structure plasticizer according to Claims 2 or 3, it is characterised in that：It is described
Step 1) in, a kind of and monoacid containing rigid ring structure in resorcinol dihydroxyethyl ether or hydroquinone two hydroxy ethyl ether
Mol ratio be 1: 2.1~2.4.
6. the preparation method according to claim 4 containing multiple rigid ring structure plasticizer, it is characterised in that：The step
1) in, a kind of and monoacid containing rigid ring structure in resorcinol dihydroxyethyl ether or hydroquinone two hydroxy ethyl ether rubs
You are than being 1: 2.1~2.4.
7. the preparation method containing multiple rigid ring structure plasticizer according to Claims 2 or 3, it is characterised in that：It is described
Step 1) in, esterification reaction temperature is controlled between 80 DEG C~130 DEG C, and reaction time of esterification control is 3~4h.
8. the preparation method containing multiple rigid ring structure plasticizer according to Claims 2 or 3, it is characterised in that：It is described
Step 2) in, the organic solvent is one kind in absolute ethyl alcohol, ether, acetone, tetrahydrofuran.
9. a kind of application in polyvinyl chloride is prepared containing multiple rigid ring structure plasticizer as claimed in claim 1, it is special
Levy and be：Polyvinyl chloride, mass ratio are prepared according to following components：Polyvinyl chloride powder: plasticizer: stabilizer=100: (30~50)
: (1~3) is mixed to get mixture, and the mixture of acquisition is carried out into banburying under conditions of 150 DEG C by banbury, finally pressed
Sample is made in piece, and the stabilizer is one kind in 2 ethyl hexanoic acid zinc, thiol-butyl tin, lead sulfate tribasic.
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| CN108034050A (en) * | 2018-01-26 | 2018-05-15 | 武汉科技大学 | A kind of plasticizer of the high molecular weight of oxygen-containing silica bridged linkage, preparation method and applications |
| WO2018155583A1 (en) * | 2017-02-27 | 2018-08-30 | パイロットインキ株式会社 | Thermochromic color memorizing composition and thermochromic color memorizing microcapsule pigment enclosing same |
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| CN101522785A (en) * | 2006-09-05 | 2009-09-02 | 吉诺维克特别控股公司 | Polymeric plasticizers for polymer compositions exhibiting high surface energy |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN101522785A (en) * | 2006-09-05 | 2009-09-02 | 吉诺维克特别控股公司 | Polymeric plasticizers for polymer compositions exhibiting high surface energy |
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| WO2018155583A1 (en) * | 2017-02-27 | 2018-08-30 | パイロットインキ株式会社 | Thermochromic color memorizing composition and thermochromic color memorizing microcapsule pigment enclosing same |
| US11384247B2 (en) | 2017-02-27 | 2022-07-12 | Kabushiki Kaisha Pilot Corporation | Thermochromic color-memory composition and thermochromic color-memory microcapsule pigment encapsulating the same |
| CN108034050A (en) * | 2018-01-26 | 2018-05-15 | 武汉科技大学 | A kind of plasticizer of the high molecular weight of oxygen-containing silica bridged linkage, preparation method and applications |
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