CN107200865B - 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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- CN107200865B CN107200865B CN201710525374.9A CN201710525374A CN107200865B CN 107200865 B CN107200865 B CN 107200865B CN 201710525374 A CN201710525374 A CN 201710525374A CN 107200865 B CN107200865 B CN 107200865B
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- 239000004014 plasticizer Substances 0.000 title claims abstract description 80
- 238000002360 preparation method Methods 0.000 title claims abstract description 24
- 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 26
- 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 Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 15
- 239000012153 distilled water Substances 0.000 claims description 14
- WPYMKLBDIGXBTP-UHFFFAOYSA-N benzoic acid Chemical compound OC(=O)C1=CC=CC=C1 WPYMKLBDIGXBTP-UHFFFAOYSA-N 0.000 claims description 12
- -1 thiol-butyl tin Chemical compound 0.000 claims description 11
- 238000006243 chemical reaction Methods 0.000 claims description 8
- 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
- 238000002156 mixing Methods 0.000 claims description 6
- 239000000843 powder Substances 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
- SMNDYUVBFMFKNZ-UHFFFAOYSA-N 2-furoic acid Chemical compound OC(=O)C1=CC=CO1 SMNDYUVBFMFKNZ-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 group 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
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 3
- 229960000935 dehydrated alcohol Drugs 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
- 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
- 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
- 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
- WBHQBSYUUJJSRZ-UHFFFAOYSA-M sodium bisulfate Chemical compound [Na+].OS([O-])(=O)=O WBHQBSYUUJJSRZ-UHFFFAOYSA-M 0.000 claims 1
- 229910000342 sodium bisulfate Inorganic materials 0.000 claims 1
- 239000000047 product Substances 0.000 abstract description 28
- 230000005012 migration Effects 0.000 abstract description 11
- 238000013508 migration Methods 0.000 abstract description 11
- 238000000746 purification Methods 0.000 abstract description 5
- 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
- 238000004566 IR spectroscopy Methods 0.000 abstract 1
- 238000005481 NMR spectroscopy Methods 0.000 abstract 1
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 16
- 238000004088 simulation Methods 0.000 description 14
- 238000012360 testing method Methods 0.000 description 14
- 210000003296 saliva Anatomy 0.000 description 13
- 210000004243 sweat Anatomy 0.000 description 13
- 238000005303 weighing Methods 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
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical compound [Na+].OC([O-])=O UIIMBOGNXHQVGW-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
- 229910000410 antimony oxide Inorganic materials 0.000 description 5
- VTRUBDSFZJNXHI-UHFFFAOYSA-N oxoantimony Chemical compound [Sb]=O VTRUBDSFZJNXHI-UHFFFAOYSA-N 0.000 description 5
- 238000010998 test method Methods 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
- 125000000217 alkyl group Chemical group 0.000 description 4
- 235000019270 ammonium chloride Nutrition 0.000 description 4
- 238000005119 centrifugation Methods 0.000 description 4
- 238000001035 drying Methods 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
- 229910000030 sodium bicarbonate Inorganic materials 0.000 description 4
- 235000017557 sodium bicarbonate Nutrition 0.000 description 4
- 230000009182 swimming Effects 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
- 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
- 238000011161 development Methods 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 150000002148 esters Chemical class 0.000 description 3
- 239000001257 hydrogen Substances 0.000 description 3
- 229910052739 hydrogen Inorganic materials 0.000 description 3
- 238000002329 infrared spectrum Methods 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
- 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
- 238000005516 engineering process Methods 0.000 description 2
- 238000002290 gas chromatography-mass spectrometry Methods 0.000 description 2
- 230000036541 health Effects 0.000 description 2
- 238000005259 measurement Methods 0.000 description 2
- 238000000034 method 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
- 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 1
- 238000005033 Fourier transform infrared spectroscopy Methods 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
- 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
- 239000006227 byproduct Substances 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 239000003795 chemical substances by application Substances 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
- 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
- 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
- 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
- 239000000463 material Substances 0.000 description 1
- 231100000956 nontoxicity Toxicity 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 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
- 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 includes by one of resorcinol dihydroxyethyl ether or hydroquinone two hydroxy ethyl ether and a kind of monoacid containing rigid ring structure, esterification is carried out under the catalytic action of catalyst and condition of high vacuum degree, plasticizer crude product is prepared, pass through the purification process in later period again, plasticizer pure substance is prepared, which passes through nuclear magnetic resonance spectroscopy, mass spectrum and infrared spectroscopy respectively and carry out structural characterization.It is prepared by the present invention to be mainly used in polyvinyl chloride resin containing multiple rigid ring structure plasticizer, the thermal stability and resistance to migration prepared by the present invention that plasticizer is not only effectively raised containing multiple rigid ring structure plasticizer, and the antistatic property 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 fields, more particularly to containing multiple rigid ring structure plasticizer and preparation method
And its application.
Background technique
Plasticizer is a kind of processability, plasticity, flexible for being added to and improving them in plastics, resin or elastomer
Property, draftability, but do not change the substance for being plasticized material basic chemical property.It is mainly used in polyvinyl chloride (PVC) resin,
Dosage in PVC can account for 98% or more of entire plasticizer consumption, therefore development and the PVC industrial expansion breath breath of plasticizer
It is related.Now domestic common plasticizer kind mainly includes phthalate, terephthalic acid ester, alkyl sulfonic acid benzene
Esters, fatty acid ester etc., yield account for about the 80% of plasticizer total amount.In recent years, with the rapid development of science and technology and
More expectations of the people to Green Chemistry, propose increasingly higher demands to the performance of plasticizer, therefore development and production are more
Plasticizer with high-performance, functionalization, nontoxicity, customizations becomes the emphasis of current plasticizer research field.
Conventional plasticizers such as dioctyl phthalate (DOP), diisononyl phthalate (DINP) etc. are to make at present
Increase amorphous region volume since it is with long alkyl chain structure with most commonly used a kind of plasticizer, increase polymerization owner
Chain moving machine meeting imparts the better processing performance of product to can significantly reduce the glass transition temperature of polymer.Together
When, long alkyl chain structure to polymer macromolecule have screen effect and lubricity, can greatly improve polymer flexibility,
Ultraviolet resistance and cold resistance.But with the continuous deepening of research, this kind of plasticizer disadvantage be also gradually exposed, it is longer
Alkyl chain structure keeps plasticizer volatility larger, and thermodynamic property is unstable, causes product intolerant to migration, after long-time use
Product surface is easy softening, tacky or even rupture, substantially reduces the using effect of product.Resistance to migration is usually and anti-pollution simultaneously
Property related, the poor product of migration usually not anti-pollution, this can also reduce the using effect of product.
Application of the universal phthalic ester plasticizer in the industries such as medical instrument, food, toy, artificial leather is got over
Come it is more extensive, other than itself has potential carcinogenicity except, and due to its long alkyl chain structure, in PVC product easily
It migrates and is extracted out by solvent, not only influence properties of product, also directly threaten the health of the mankind.
Summary of the invention
Existing plasticizer technology is easy to migrate due to being caused using universal phthalic ester plasticizer, easily enters quilt
In the solvent (such as water, alcohols) of extracting, the health of user is influenced.
In order to solve the above technical problems, the invention discloses the preparation methods 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 thermal stability and
Resistance to migration, and the antistatic property of PVC product is improved well, greatly expand the use scope of PVC product.
To achieve the above object, the present invention provides containing multiple rigid ring structure plasticizer, molecular structural formula such as Formulas I or formula
Shown in II:
Group R in Formulas I or Formula II is selected from one of phenyl, cyclopenta, cyclohexyl, furyl.
Technical solution to better implement the present invention, the invention also discloses the systems containing multiple rigid ring structure plasticizer
Preparation Method includes the following steps:
1) prepare plasticizer crude product: by one of resorcinol dihydroxyethyl ether or hydroquinone two hydroxy ethyl ether with
A kind of monoacid containing rigid ring structure is placed in reaction vessel, carries out being esterified under the catalytic action and low pressure of catalyst anti-
It answers, 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 object, the molecular formula of the plasticizer is as shown in above-mentioned Formulas I or Formula II；
2) it purifies plasticizer crude product: the plasticizer crude product that the step 1) is prepared being washed with distilled water, mistake
Filter at least three times, then is recrystallized with organic solvent, is finally centrifuged, is filtered again, dried plasticizer, neat is prepared
Net object, the plasticizer pure substance are the main product as shown in above-mentioned Formulas I or Formula II of molecular formula.
Further, in the step 1), the monoacid containing rigid ring structure is cyclopentane-carboxylic acid, benzoic acid, ring
One of hexane formic acid, 2- furancarboxylic acid.
Still further, the catalyst is tetraisopropyl titanate, copper p-toluenesulfonate, hydrogen sulfate in the step 1)
One of sodium, Sodium Bisulfate Monohydrate, antimony oxide, the dosage of the catalyst are the unitary acid substance containing rigid ring structure
Amount 1%~2%.
Further, in the step 1), in resorcinol dihydroxyethyl ether or hydroquinone two hydroxy ethyl ether one
Kind and the molar ratio of the monoacid containing rigid ring structure are 1: 2.1~2.4.
Further, in the step 1), esterification reaction temperature control is at 80 DEG C~130 DEG C, reaction time of esterification control
It is made as 3~4h.
Further, in the step 2), the organic solvent is dehydrated alcohol, in ether, acetone, tetrahydrofuran
It is a kind of.
It is prepared by the present invention to prepare the application in polyvinyl chloride containing multiple rigid ring structure plasticizer, according to following components
Prepare polyvinyl chloride, mass ratio are as follows: polyvinyl chloride powder: plasticizer: stabilizer=100: (30~50): (1~3) is mixed to get mixed
Object is closed, the mixture of acquisition is subjected to mixing by mixer under conditions of 150 DEG C, polyvinyl chloride sample is made in last tabletting
Product, the stabilizer are one of 2 ethyl hexanoic acid zinc, thiol-butyl tin, lead sulfate tribasic.
Simultaneously in order to carry out structural characterization to plasticizer product prepared by the present invention, nucleus magnetic hydrogen spectrum, mass spectrum have been carried out respectively
And examination of infrared spectrum, it is as follows to test the instrument used:
It is provided by the invention containing multiple rigid ring structure plasticizer1H-NMR uses 400 core of Bruker Avance DMX
Magnetic resonance device, TMS is as internal standard, CDCl3Make solvent；
Infrared spectrum analysis uses FTIR-650 Fourier Transform Infrared Spectrometer, and test method is using pressing potassium bromide troche
Method, in 400-4000cm-1The skeletal vibration infrared absorption peak of record sample in range；
7890A/5975C gas chromatography mass spectrometry chromatograph of the mass spectral analysis using U.S. Agilent company, 1.0 μ L of sample volume, into
250 DEG C of sample mouth temperature, HP-5MS capillary chromatographic column, column temperature initial temperature are 50 DEG C, rise to 240 DEG C with 10 DEG C/min, keep
1min。
The utility model has the advantages that
1, the plasticizer that is prepared of the present invention introduces rigid ring structure, effectively raise plasticizer thermal stability and
Resistance to migration；
2, the plasticizer that the present invention is prepared can improve the antistatic property of PVC product well, greatly expand PVC system
The use scope of product；
3, preparation method of the invention is simple, and income is higher.
Detailed description of the invention
Fig. 1 is hydroquinone two hydroxy ethyl ether-benzoic acid diester nucleus magnetic hydrogen spectrum figure of preparation of the embodiment of the present invention；
Fig. 2 is the hydroquinone two hydroxy ethyl ether-benzoic acid diester mass spectrogram prepared in Fig. 1；
Fig. 3 is resorcinol dihydroxyethyl ether-benzoic acid diester infrared spectrogram of preparation of the embodiment of the present invention.
Specific embodiment
In order to better explain the present invention, below in conjunction with specific embodiments and drawings the present invention is furture elucidated it is main in
Hold, but the contents of the present invention are not limited solely to following embodiment.
Embodiment 1: plasticizer is prepared using hydroquinone two hydroxy ethyl ether and benzoic acid as raw material:
Esterification prepares crude product: the benzoic acid of 4.396g, pair of 3.033g are sequentially added in 50ml single-necked flask
The antimony oxide of benzenediol dihydroxyethyl ether and 0.08g is gradually warmed up after being completely dissolved reactant to 85 DEG C and passes through circulation
Ability of swimming vacuum pump, which vacuumizes, makes the pressure in single-necked flask keep 100Pa or so, and temperature control is 90 DEG C of reactions 3 hours, finally
It increases the temperature to 120 DEG C to react 1 hour, after stopping heating, cooled to room temperature obtains plasticizer crude product 6.919g.On
The chemical equation for stating reaction is as follows:
The separation and purification of crude product: gained plasticizer crude product after reaction is washed with distilled water filtering three times, then
It is recrystallized with dehydrated alcohol, the plasticizer product 5.841g finally refined after centrifugation, filtering, drying, yield
It is 78.62%.
In order to further verify benzenediol dihydroxyethyl ether-benzoic ether manufactured in the present embodiment, use1H-NMR and
GC-MS characterizes product manufactured in the present embodiment, has respectively obtained Fig. 1 and Fig. 2, in conjunction with Fig. 1 it is found that Fig. 1 hydroquinone
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 dosage: 100 parts of PVC powder, plasticising prepared by above-described embodiment 1
30 parts of agent, 1 part of 2 ethyl hexanoic acid zinc, controlled at 150 DEG C of progress mixings, then tabletting in mixer.
Simulation prepares sweat: weighing sodium bicarbonate 4g, sodium chloride 0.5g, potassium carbonate 0.35g is arrived with distilled water constant volume
1000ml is to get the simulated sweat for being 8.8 to pH.
Simulation preparation saliva: weighing sodium chloride 4.5g, potassium chloride 0.3g, ammonium chloride 0.4g, 90% lactic acid urea 0.2g,
With distilled water constant volume to 1000ml to get the simulation saliva for being 3.04 to pH.
It takes PVC tabletting to be respectively put into Simulated sweat and saliva, impregnates 30 minutes at room temperature, carry out resistance to migration survey
Examination compares the size of mobility by weighing the tablet quality before and after impregnating, and test result is as shown in table 1.Separately take PVC tabletting
Resistivity measurement is carried out, the test method of resistivity meets GB/T1410-1989 standard, 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: the benzoic acid of 4.396g is sequentially added in 50ml single-necked flask, between 3.033g
The antimony oxide of benzenediol dihydroxyethyl ether and 0.08g is gradually warmed up after being completely dissolved reactant to 85 DEG C and passes through circulation
Ability of swimming vacuum pump, which vacuumizes, makes the pressure in single-necked flask keep 100Pa or so, and temperature control is reacted 3 hours for 90 DEG C.Finally
It increases the temperature to 120 DEG C to react 1 hour, stops heating and allow its cooled to room temperature, obtain plasticizer crude product 7.095g
The separation and purification of crude product: products therefrom after reaction is washed with distilled water filtering three times, then with anhydrous second
Alcohol is recrystallized, the plasticizer product 5.677g finally refined after centrifugation, filtering, drying, and yield is
76.42%.
In order to further verify resorcinol dihydroxyethyl ether-benzoic acid diester manufactured in the present embodiment, use is infrared
Spectrum characterizes 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 vibration in 1162cm-1Place absorbs, while in 3467cm-1Place is without there is apparent hydroxyl absorption peak, so can
Expected esterification has occurred to say, and generates expected product.
Prepare PVC tabletting: by following components dosage: 100 parts of PVC powder, 30 parts of the implementation case plasticizer, 2 ethyl hexanoic acid
1 part of zinc, 150 DEG C of mixings, tabletting.
Simulation prepares sweat: weighing and takes sodium bicarbonate 4g, sodium chloride 0.5g, potassium carbonate 0.35g is arrived with distilled water constant volume
1000ml is to get the simulated sweat for being 8.8 to pH.
Simulation preparation saliva: weighing sodium chloride 4.5g, potassium chloride 0.3g, ammonium chloride 0.4g, 90% lactic acid urea 0.2g,
With distilled water constant volume to 1000ml to get the simulation saliva for being 3.04 to pH.
It takes the PVC tabletting prepared to be respectively put into Simulated sweat and saliva, impregnates 30 minutes at room temperature, carry out resistance to
Migration test compares the size of mobility by weighing the tablet quality before and after impregnating, and test result is as shown in table 1.Separately
Pressure piece carries out resistivity measurement, and the test method of resistivity meets GB/T1410-1989 standard, 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: the naphthenic acid of 4.614g, 3.033g are sequentially added in 50ml single-necked flask
Hydroquinone two hydroxy ethyl ether and 0.1g antimony oxide, be gradually warmed up after being completely dissolved reactant to 85 DEG C by following
Ring ability of swimming vacuum pump, which vacuumizes, makes the pressure in single-necked flask keep 100Pa or so, and temperature control is reacted 3 hours for 90 DEG C.Most
After increase the temperature to 120 DEG C and react 1 hour, stop heating and allow its cooled to room temperature, obtain plasticizer crude product 7.102g.
The separation and purification of crude product: products therefrom after reaction is washed with distilled water filtering three times, then with anhydrous second
Alcohol is recrystallized, the plasticizer product 5.904g finally refined after centrifugation, filtering, drying, and yield is
77.21%.
Prepare PVC tabletting: by following components dosage: 100 parts of PVC powder, 30 parts of the implementation case plasticizer, 2 ethyl hexanoic acid
1 part of zinc, 150 DEG C of mixings, tabletting.
Simulation prepares sweat: weighing and takes sodium bicarbonate 4g, sodium chloride 0.5g, potassium carbonate 0.35g is arrived with distilled water constant volume
1000ml is to get the simulated sweat for being 8.8 to pH.
Simulation preparation saliva: weighing sodium chloride 4.5g, potassium chloride 0.3g, ammonium chloride 0.4g, 90% lactic acid urea 0.2g,
With distilled water constant volume to 1000ml to get the simulation saliva for being 3.04 to pH.
Pressure piece is respectively put into Simulated sweat and saliva, is impregnated 30 minutes at room temperature, and resistance to migration test is carried out,
Compare the size of mobility by weighing the tablet quality before and after impregnating, test result is as shown in table 1.Another pressure piece carries out electricity
The test of resistance rate, the test method of resistivity meet GB/T1410-1989 standard, 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: the naphthenic acid of 4.614g, 3.033g are sequentially added in 50ml single-necked flask
Hydroquinone two hydroxy ethyl ether and 0.1g antimony oxide, be gradually warmed up after being completely dissolved reactant to 85 DEG C by following
Ring ability of swimming vacuum pump, which vacuumizes, makes the pressure in single-necked flask keep 100Pa or so, and temperature control is reacted 3 hours for 90 DEG C.Most
After increase the temperature to 120 DEG C and react 1 hour, stop heating and allow its cooled to room temperature, obtain plasticizer crude product 6.985g.
The separation and purification of crude product: products therefrom after reaction is washed with distilled water filtering three times, then with anhydrous second
Alcohol is recrystallized, the plasticizer product 6.005g finally refined after centrifugation, filtering, drying, and yield is
78.53%.
Prepare PVC tabletting: by following components dosage: 100 parts of PVC powder, 30 parts of the implementation case plasticizer, 2 ethyl hexanoic acid
1 part of zinc, 150 DEG C of mixings, tabletting.
Simulation prepares sweat: weighing and takes sodium bicarbonate 4g, sodium chloride 0.5g, potassium carbonate 0.35g is arrived with distilled water constant volume
1000ml is to get the simulated sweat for being 8.8 to pH.
Simulation preparation saliva: weighing sodium chloride 4.5g, potassium chloride 0.3g, ammonium chloride 0.4g, 90% lactic acid urea 0.2g,
With distilled water constant volume to 1000ml to get the simulation saliva for being 3.04 to pH.
Pressure piece is respectively put into Simulated sweat and saliva, is impregnated 30 minutes at room temperature, and resistance to migration test is carried out,
Compare the size of mobility by weighing the tablet quality before and after impregnating, test result is as shown in table 1.Another pressure piece carries out electricity
The test of resistance rate, the test method of resistivity meet GB/T1410-1989 standard, and test result is as shown in table 2.
The plasticizer of 1 1~embodiment of embodiment 4 of table preparation is compared with the resistance to mobility 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 have preferable resistance to migration.
The plasticizer of 2 1~embodiment of embodiment 4 of table preparation is compared with DOP resistance
As can be seen from Table 2, plasticizer prepared by the present invention has relatively higher resistance compared to DOP, increases PVC system
The electrical insulating property and antistatic property of product.
Above embodiments are only best citing, rather than a limitation of the embodiments of the present invention.Except above-described embodiment
Outside, there are also other embodiments by the present invention.All technical solutions formed using equivalent substitution or equivalent transformation, all fall within the present invention
It is required that protection scope in.
Claims (9)
1. one kind is containing 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 selected from one of cyclopenta, cyclohexyl, furyl.
2. a kind of preparation method containing multiple rigid ring structure plasticizer, characterized by the following steps:
1) plasticizer crude product is prepared: by one of 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 the absolute pressure of 50~200pa
Esterification is carried out, plasticizer crude product is prepared；
2) it purifies plasticizer crude product: the plasticizer crude product that the step 1) is prepared being washed with distilled water, is filtered extremely
It is few then to be recrystallized three times with organic solvent, it is finally centrifuged, filtered again, dried plasticizer pure substance is prepared.
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 cyclopentane-carboxylic acid, benzoic acid, naphthenic acid, one in 2- furancarboxylic acid
Kind.
4. the preparation method according to claim 2 or 3 containing multiple rigid ring structure plasticizer, it is characterised in that: described
In step 1), the catalyst is tetraisopropyl titanate, copper p-toluenesulfonate, sodium bisulfate, Sodium Bisulfate Monohydrate, three oxidations two
One of antimony, the dosage of the catalyst are the 1%~2% of the amount of the unitary acid substance containing rigid ring structure.
5. the preparation method according to claim 2 or 3 containing multiple rigid ring structure plasticizer, it is characterised in that: described
In step 1), one of resorcinol dihydroxyethyl ether or hydroquinone two hydroxy ethyl ether and the monoacid containing rigid ring structure
Molar 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, one of resorcinol dihydroxyethyl ether or hydroquinone two hydroxy ethyl ether rub with the monoacid containing rigid ring structure
You are than being 1: 2.1~2.4.
7. the preparation method according to claim 2 or 3 containing multiple rigid ring structure plasticizer, it is characterised in that: described
In step 1), 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 according to claim 2 or 3 containing multiple rigid ring structure plasticizer, it is characterised in that: described
In step 2), the organic solvent is one of dehydrated alcohol, ether, acetone, tetrahydrofuran.
9. a kind of preparing the application in polyvinyl chloride containing multiple rigid ring structure plasticizer as described in claim 1, special
Sign is: preparing polyvinyl chloride according to following components, mass ratio: polyvinyl chloride powder: plasticizer: stabilizer=100: (30~50)
: (1~3) is mixed to get mixture, and the mixture of acquisition is carried out mixing under conditions of 150 DEG C by mixer, is finally pressed
Sample is made in piece, and the stabilizer is one of 2 ethyl hexanoic acid zinc, thiol-butyl tin, lead sulfate tribasic.
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