CN106892941A - A kind of method that utilization industrial by-product terpinene prepares fluorine-containing demoulding additive - Google Patents
A kind of method that utilization industrial by-product terpinene prepares fluorine-containing demoulding additive Download PDFInfo
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- 229930006978 terpinene Natural products 0.000 title claims abstract description 64
- 150000003507 terpinene derivatives Chemical class 0.000 title claims abstract description 60
- 239000000654 additive Substances 0.000 title claims abstract description 38
- 230000000996 additive effect Effects 0.000 title claims abstract description 38
- 229910052731 fluorine Inorganic materials 0.000 title claims abstract description 23
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 title claims abstract description 22
- 239000011737 fluorine Substances 0.000 title claims abstract description 22
- 239000006227 byproduct Substances 0.000 title claims abstract description 19
- 238000000034 method Methods 0.000 title claims abstract description 9
- 239000000047 product Substances 0.000 claims abstract description 60
- 239000002253 acid Substances 0.000 claims abstract description 25
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims abstract description 24
- YHQGMYUVUMAZJR-UHFFFAOYSA-N α-terpinene Chemical compound CC(C)C1=CC=C(C)CC1 YHQGMYUVUMAZJR-UHFFFAOYSA-N 0.000 claims abstract description 24
- HCDGVLDPFQMKDK-UHFFFAOYSA-N hexafluoropropylene Chemical group FC(F)=C(F)C(F)(F)F HCDGVLDPFQMKDK-UHFFFAOYSA-N 0.000 claims abstract description 23
- 238000006384 oligomerization reaction Methods 0.000 claims abstract description 23
- 150000001875 compounds Chemical class 0.000 claims abstract description 22
- 125000003342 alkenyl group Chemical group 0.000 claims abstract description 21
- 230000032050 esterification Effects 0.000 claims abstract description 21
- 238000005886 esterification reaction Methods 0.000 claims abstract description 21
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims abstract description 20
- 238000006735 epoxidation reaction Methods 0.000 claims abstract description 18
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims abstract description 13
- 238000006467 substitution reaction Methods 0.000 claims abstract description 13
- WSTYNZDAOAEEKG-UHFFFAOYSA-N Mayol Natural products CC1=C(O)C(=O)C=C2C(CCC3(C4CC(C(CC4(CCC33C)C)=O)C)C)(C)C3=CC=C21 WSTYNZDAOAEEKG-UHFFFAOYSA-N 0.000 claims abstract description 12
- MOYAFQVGZZPNRA-UHFFFAOYSA-N Terpinolene Chemical compound CC(C)=C1CCC(C)=CC1 MOYAFQVGZZPNRA-UHFFFAOYSA-N 0.000 claims abstract description 10
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims abstract description 10
- ZBCBWPMODOFKDW-UHFFFAOYSA-N diethanolamine Chemical compound OCCNCCO ZBCBWPMODOFKDW-UHFFFAOYSA-N 0.000 claims abstract description 10
- 229940043237 diethanolamine Drugs 0.000 claims abstract description 10
- XMGQYMWWDOXHJM-UHFFFAOYSA-N limonene Chemical compound CC(=C)C1CCC(C)=CC1 XMGQYMWWDOXHJM-UHFFFAOYSA-N 0.000 claims abstract description 10
- 238000011938 amidation process Methods 0.000 claims abstract description 8
- 238000010534 nucleophilic substitution reaction Methods 0.000 claims abstract description 8
- 238000006317 isomerization reaction Methods 0.000 claims abstract description 5
- 238000007259 addition reaction Methods 0.000 claims abstract description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 32
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N dimethyl sulfoxide Natural products CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 claims description 20
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 14
- 238000006243 chemical reaction Methods 0.000 claims description 13
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 10
- QAOWNCQODCNURD-UHFFFAOYSA-N sulfuric acid Substances OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 8
- 229960000583 acetic acid Drugs 0.000 claims description 7
- 239000012362 glacial acetic acid Substances 0.000 claims description 7
- 230000000694 effects Effects 0.000 claims description 6
- JOXIMZWYDAKGHI-UHFFFAOYSA-N toluene-4-sulfonic acid Chemical compound CC1=CC=C(S(O)(=O)=O)C=C1 JOXIMZWYDAKGHI-UHFFFAOYSA-N 0.000 claims description 6
- 239000012065 filter cake Substances 0.000 claims description 5
- 239000008236 heating water Substances 0.000 claims description 5
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 5
- 239000002904 solvent Substances 0.000 claims description 5
- SVYKKECYCPFKGB-UHFFFAOYSA-N N,N-dimethylcyclohexylamine Chemical compound CN(C)C1CCCCC1 SVYKKECYCPFKGB-UHFFFAOYSA-N 0.000 claims description 4
- 238000001914 filtration Methods 0.000 claims description 4
- LNOPIUAQISRISI-UHFFFAOYSA-N n'-hydroxy-2-propan-2-ylsulfonylethanimidamide Chemical compound CC(C)S(=O)(=O)CC(N)=NO LNOPIUAQISRISI-UHFFFAOYSA-N 0.000 claims description 4
- YWEUIGNSBFLMFL-UHFFFAOYSA-N diphosphonate Chemical compound O=P(=O)OP(=O)=O YWEUIGNSBFLMFL-UHFFFAOYSA-N 0.000 claims description 2
- DLYUQMMRRRQYAE-UHFFFAOYSA-N phosphorus pentoxide Inorganic materials O1P(O2)(=O)OP3(=O)OP1(=O)OP2(=O)O3 DLYUQMMRRRQYAE-UHFFFAOYSA-N 0.000 claims description 2
- 239000003795 chemical substances by application Substances 0.000 description 16
- 230000008901 benefit Effects 0.000 description 7
- -1 polysiloxane Polymers 0.000 description 7
- 238000003756 stirring Methods 0.000 description 6
- 239000000463 material Substances 0.000 description 4
- 239000003921 oil Substances 0.000 description 4
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 3
- 150000002430 hydrocarbons Chemical class 0.000 description 3
- 229910052698 phosphorus Inorganic materials 0.000 description 3
- 239000011574 phosphorus Substances 0.000 description 3
- 238000010992 reflux Methods 0.000 description 3
- 238000011160 research Methods 0.000 description 3
- RBNWAMSGVWEHFP-UHFFFAOYSA-N trans-p-Menthane-1,8-diol Chemical compound CC(C)(O)C1CCC(C)(O)CC1 RBNWAMSGVWEHFP-UHFFFAOYSA-N 0.000 description 3
- 238000010792 warming Methods 0.000 description 3
- NIONDZDPPYHYKY-UHFFFAOYSA-N 2-hexenoic acid Chemical class CCCC=CC(O)=O NIONDZDPPYHYKY-UHFFFAOYSA-N 0.000 description 2
- 239000001293 FEMA 3089 Substances 0.000 description 2
- 150000007513 acids Chemical class 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 229920001971 elastomer Polymers 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 150000003961 organosilicon compounds Chemical class 0.000 description 2
- 229920000642 polymer Polymers 0.000 description 2
- 238000010094 polymer processing Methods 0.000 description 2
- 229920001296 polysiloxane Polymers 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- IIACRCGMVDHOTQ-UHFFFAOYSA-N sulfamic acid group Chemical group S(N)(O)(=O)=O IIACRCGMVDHOTQ-UHFFFAOYSA-N 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- RSWGJHLUYNHPMX-UHFFFAOYSA-N Abietic-Saeure Natural products C12CCC(C(C)C)=CC2=CCC2C1(C)CCCC2(C)C(O)=O RSWGJHLUYNHPMX-UHFFFAOYSA-N 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical class [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 239000006057 Non-nutritive feed additive Substances 0.000 description 1
- 229910019142 PO4 Inorganic materials 0.000 description 1
- KHPCPRHQVVSZAH-HUOMCSJISA-N Rosin Natural products O(C/C=C/c1ccccc1)[C@H]1[C@H](O)[C@@H](O)[C@@H](O)[C@@H](CO)O1 KHPCPRHQVVSZAH-HUOMCSJISA-N 0.000 description 1
- RAHZWNYVWXNFOC-UHFFFAOYSA-N Sulphur dioxide Chemical class O=S=O RAHZWNYVWXNFOC-UHFFFAOYSA-N 0.000 description 1
- 239000011149 active material Substances 0.000 description 1
- 150000001336 alkenes Chemical class 0.000 description 1
- 125000003368 amide group Chemical group 0.000 description 1
- 239000012620 biological material Substances 0.000 description 1
- 238000004939 coking Methods 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 239000000806 elastomer Substances 0.000 description 1
- 239000005447 environmental material Substances 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- 125000001153 fluoro group Chemical group F* 0.000 description 1
- 239000004519 grease Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 230000008676 import Effects 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 239000008204 material by function Substances 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 1
- SNGREZUHAYWORS-UHFFFAOYSA-N perfluorooctanoic acid Chemical compound OC(=O)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)F SNGREZUHAYWORS-UHFFFAOYSA-N 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
- 239000004033 plastic Substances 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 229920002635 polyurethane Polymers 0.000 description 1
- 239000004814 polyurethane Substances 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 238000009987 spinning Methods 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- KHPCPRHQVVSZAH-UHFFFAOYSA-N trans-cinnamyl beta-D-glucopyranoside Natural products OC1C(O)C(O)C(CO)OC1OCC=CC1=CC=CC=C1 KHPCPRHQVVSZAH-UHFFFAOYSA-N 0.000 description 1
- 239000000341 volatile oil Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F9/00—Compounds containing elements of Groups 5 or 15 of the Periodic Table
- C07F9/02—Phosphorus compounds
- C07F9/06—Phosphorus compounds without P—C bonds
- C07F9/08—Esters of oxyacids of phosphorus
- C07F9/09—Esters of phosphoric acids
- C07F9/11—Esters of phosphoric acids with hydroxyalkyl compounds without further substituents on alkyl
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C33/00—Moulds or cores; Details thereof or accessories therefor
- B29C33/56—Coatings, e.g. enameled or galvanised; Releasing, lubricating or separating agents
- B29C33/60—Releasing, lubricating or separating agents
- B29C33/62—Releasing, lubricating or separating agents based on polymers or oligomers
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C231/00—Preparation of carboxylic acid amides
- C07C231/02—Preparation of carboxylic acid amides from carboxylic acids or from esters, anhydrides, or halides thereof by reaction with ammonia or amines
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C5/00—Preparation of hydrocarbons from hydrocarbons containing the same number of carbon atoms
- C07C5/22—Preparation of hydrocarbons from hydrocarbons containing the same number of carbon atoms by isomerisation
- C07C5/23—Rearrangement of carbon-to-carbon unsaturated bonds
- C07C5/25—Migration of carbon-to-carbon double bonds
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C5/00—Preparation of hydrocarbons from hydrocarbons containing the same number of carbon atoms
- C07C5/22—Preparation of hydrocarbons from hydrocarbons containing the same number of carbon atoms by isomerisation
- C07C5/27—Rearrangement of carbon atoms in the hydrocarbon skeleton
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C51/00—Preparation of carboxylic acids or their salts, halides or anhydrides
- C07C51/347—Preparation of carboxylic acids or their salts, halides or anhydrides by reactions not involving formation of carboxyl groups
- C07C51/353—Preparation of carboxylic acids or their salts, halides or anhydrides by reactions not involving formation of carboxyl groups by isomerisation; by change of size of the carbon skeleton
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C51/00—Preparation of carboxylic acids or their salts, halides or anhydrides
- C07C51/347—Preparation of carboxylic acids or their salts, halides or anhydrides by reactions not involving formation of carboxyl groups
- C07C51/367—Preparation of carboxylic acids or their salts, halides or anhydrides by reactions not involving formation of carboxyl groups by introduction of functional groups containing oxygen only in singly bound form
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D303/00—Compounds containing three-membered rings having one oxygen atom as the only ring hetero atom
- C07D303/02—Compounds containing oxirane rings
- C07D303/38—Compounds containing oxirane rings with hydrocarbon radicals, substituted by carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals
- C07D303/40—Compounds containing oxirane rings with hydrocarbon radicals, substituted by carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals by ester radicals
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- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Engineering & Computer Science (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Health & Medical Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Biochemistry (AREA)
- General Health & Medical Sciences (AREA)
- Molecular Biology (AREA)
- Mechanical Engineering (AREA)
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
Abstract
The invention discloses a kind of method that utilization industrial by-product terpinene prepares fluorine-containing demoulding additive, it is characterized in that：Australene in terpinene, dipentene and terpinolene are isomerizated into α-terpinene, the main component α-terpinene and continuous isomerization in terpinene and come terpinene with（Methyl）Alkenyl acid carries out addition reaction, generation（Methyl）Alkenyl acid terpinene additive compound, epoxidation reaction is carried out with hydrogen peroxide, generates epoxidation（Methyl）Alkenyl acid terpinene additive compound, it is hydrolyzed again, the double hydroxy products of generation, double hydroxy products carry out nucleophilic substitution with oligomerization of hexafluoropropylene body, the product of oligomerization of hexafluoropropylene body substitution is obtained, the product of oligomerization of hexafluoropropylene body substitution carries out amidation process, amidated products are obtained with diethanol amine, finally, amidated products carry out esterification and esterification products are obtained with phosphoric acid；As fluorine-containing demoulding additive is prepared using industrial by-product terpinene.
Description
Technical field
The present invention relates to demoulding additive synthesis technical field, the method that espespecially a kind of utilization industrial by-product terpinene prepares fluorine-containing demoulding additive.
Background technology
Releasing agent is a kind of functional materials between mould and polymer or other products,It is to prevent rubber,The mechanograph of the elastomer substances such as plastics and polyurethane and other materials,Laminated product,The materials such as spinning part are bonded on mould or metal plate,Play the class processing aid for being easy to disengaging effect,In high molecular polymer manufacture field,The use of releasing agent is essential,It is typically used as the active material predominantly hydrocarbon compound or polysiloxane-based organo-silicon compound of main releasing agent,The releasing agent abundance that hydrocarbon compound is prepared,It is cheap,Product after the demoulding can directly carry out secondary operation,But,Long-term use can cause die surface to form brown coking material and then pollute mould,The releasing agent that polysiloxane-based organo-silicon compound are prepared,Its stripping result is superior compared with the releasing agent that hydrocarbon compound is prepared,But,Certain grease can be produced on product surface after the demoulding,The suitability for secondary processing of product is poor.
Fluorine releasing agent is that compared with other kinds of releasing agent, the advantage of fluorine releasing agent mainly has with main body fluorochemical and a kind of mixture of other supplies mixed preparings：Steady quality, product storage cycle are long in itself for releasing agent；Concentration is low, and effect is good, long lifespan, and once spraying can be used for multiple times；There is good release property to high viscosity feedstock, the pollution after the demoulding to product is small, the secondary operation of product is not influenceed；Stripping result is 3-5 times of general organosilicon series releasing agent, and some external companies and research institution have carried out substantial amounts of research to fluorine releasing agent, and the report that the country researches and develops to this is less, existing efficient fluorine releasing agent substantially dependence on import.With society and the raising of environmental requirement, the pungent sulphonyl class compound of traditional perfluor and perfluorooctanoic acid compound are limited the use of or disabled because there is harm to environmental and biological materials.
It is Material synthesis terpinol with turpentine oil, a large amount of by-product terpinenes can be produced, by-product terpinene accounts for the 20%~30% of terpinol yield, China's resin resource enriches, and is one of country that rosin is fragrant and turpentine oil yield is maximum, the by-product terpinene enormous amount for being produced because synthesizing terpinol every year, terpinene is the mixture of the extremely similar isomer of various properties, separation is highly difficult, so can only be used as low-grade solvent, it is difficult to produce bigger economic benefit.
For the deficiency of domestic existing releasing agent, Selection utilization industrial by-product terpinene prepares fluorine-containing demoulding additive, the need for improving high molecular polymer processing efficiency, meeting market, with good economic benefit and social benefit.
The content of the invention
It is an object of the invention to provide a kind of method that utilization industrial by-product terpinene prepares fluorine-containing demoulding additive.
To achieve these goals, technical solution of the invention is：Australene in terpinene, dipentene and terpinolene are isomerizated into α-terpinene, the main component α-terpinene and continuous isomerization in terpinene and come terpinene with（Methyl）Alkenyl acid carries out addition reaction, generation（Methyl）Alkenyl acid terpinene additive compound, epoxidation reaction is carried out with hydrogen peroxide, generates epoxidation（Methyl）Alkenyl acid terpinene additive compound, it is hydrolyzed again, the double hydroxy products of generation, double hydroxy products carry out nucleophilic substitution with oligomerization of hexafluoropropylene body, obtain the product of oligomerization of hexafluoropropylene body substitution, and the product of oligomerization of hexafluoropropylene body substitution carries out amidation process with diethanol amine, amidated products are obtained, finally, amidated products carry out esterification and esterification products are obtained with phosphoric acid, and specific preparation method is comprised the steps of：
1) p-methyl benzenesulfonic acid and sulfamic acid effect under, the australene in terpinene system（ⅠA）, dipentene（ⅠB）And terpinolene（ⅠC）It is isomerizated into α-terpinene（Ⅱ）, the main component α-terpinene in terpinene（Ⅱ）With continuous isomerization and come α-terpinene（Ⅱ）With（Methyl）Alkenyl acid（Ⅲ）In back flow reaction 4~6 hours at 150 DEG C~180 DEG C, generation（Methyl）Alkenyl acid terpinene additive compound（ⅣA）With（ⅣB）, its main chemical reactions is：
2) under glacial acetic acid and concentrated sulfuric acid effect,（Methyl）Alkenyl acid terpinene additive compound（ⅣA）With（ⅣB）Epoxidation is generated with hydrogen peroxide in epoxidation reaction 4~5 hours at 60~80 DEG C（Methyl）Alkenyl acid terpinene additive compound（ⅤA）With（ⅤB）, its main chemical reactions is：
3) epoxidations（Methyl）Alkenyl acid terpinene additive compound（ⅤA）With（ⅤB）, it is hydrolyzed with the hot water of 3 times of volumes, stand, oil reservoir is taken, obtain double hydroxy products（ⅥA）With（ⅥB）, its main chemical reactions is：
4) is with toluene as solvent, in the presence of N, N- dimethyl cyclohexyl amine, at 20 DEG C~35 DEG C, and double hydroxy products（ⅥA）With（ⅥB）With oligomerization of hexafluoropropylene body（Ⅶ）After carrying out nucleophilic substitution 6~8 hours, toluene is distilled out,Obtain the product of oligomerization of hexafluoropropylene body substitution（ⅧA）With（ⅧB）, its main chemical reactions is：
5) product of oligomerization of hexafluoropropylene body substitution（ⅧA）With（ⅧB）And diethanol amine（Ⅸ）, amidation process is carried out at a temperature of 85 DEG C~105 DEG C, amidated products are obtained（ⅩA）With（ⅩB）, 10 DEG C~30 DEG C are cooled to, its main chemical reactions is：
6) with N, N- dimethyl sulfoxide (DMSO)s are solvent to, in the presence of phosphorus pentoxide, amidated products（ⅩA）With（ⅩB）And phosphoric acid, after heating water bath carries out esterification 3~4 hours in 85 DEG C~95 DEG C, 10 DEG C~30 DEG C are cooled to, esterification products is obtained（ⅫA）With（ⅫB）, dilute with water esterification products（ⅫA）With（ⅫB）, filter, filter cake is taken, fluorine-containing demoulding additive as is prepared using industrial by-product terpinene, its main chemical reactions is：
It is further that the R in above-mentioned each reaction equation is hydrogen, methyl, ethyl or propyl group；
R in above-mentioned each reaction equationfIt is the compound with following chemical constitution：
The group formed after a fluorine atom is lost, wherein, n=2,3,4；
Described terpinene,（Methyl）The mass ratio of alkenyl acid, hydrogen peroxide, oligomerization of hexafluoropropylene body, diethanol amine and phosphoric acid is the ﹕ 1.4~1.6 of 1 ﹕, 0.6~0.8 ﹕, 0.7~0.9 ﹕, 3.5~4.0 ﹕ 0.8~1.0；
Described p-methyl benzenesulfonic acid and sulfamic acid, its consumption is respectively the 0%~6% of terpinene quality, and its total consumption is the 6%~10% of terpinene quality；
Described glacial acetic acid and the concentrated sulfuric acid, its consumption is respectively the 20%~30% and 2%~3% of hydrogen peroxide quality；
Described N, N- dimethyl cyclohexyl amine, its consumption are the 3%~5% of terpinene quality.
The method that a kind of utilization industrial by-product terpinene of the present invention prepares fluorine-containing demoulding additive, its feature and advantage are：Selection utilization industrial by-product terpinene prepares fluorine-containing demoulding additive, and sufficient raw, cost is relatively low；Synthetic is a kind of fluorine-containing amide groups binary phosphate demoulding additive, belongs to fluorine-containing high-end demoulding agent addition agent, the need for can improving high molecular polymer processing efficiency, meeting market；With good economic benefit and social benefit；Operation is simple and easy to apply, is adapted to industrialized production.
Specific embodiment
Embodiment 1
Equipped with agitating device,In the four-hole bottle of reflux condensate device and thermometer,Add 30 grams of terpinenes,1.5 grams of toluene sulfonic acides and 0.5 gram of concentrated sulfuric acid,After stirring 0.5~1 hour,Add 21 grams of 2- methyl -2- penetenoic acids,Being warming up to 170 DEG C~180 DEG C carries out back flow reaction 5 hours,Generation methylpent olefin(e) acid terpinene additive compound,It is cooled to 60~70 DEG C,Add 25 grams of hydrogen peroxide,5 grams of glacial acetic acid and 0.5 gram of concentrated sulfuric acid,Carry out epoxidation reaction 4 hours,Generation epoxidation 2- methyl -2- penetenoic acid terpinene additive compounds,Then it is hydrolyzed with the hot water of 3 times of volumes,Stand,Take oil reservoir,The double hydroxy products of generation,Add 150mL toluene and 120 grams of oligomerization of hexafluoropropylene bodies,Open stirring,It is slowly added to 1.5 grams of N,N- dimethyl cyclohexyl amines,After nucleophilic substitution being carried out at a temperature of 20 DEG C~35 DEG C 6~8 hours,Distill out toluene,Obtain the product of oligomerization of hexafluoropropylene body substitution,To 30 grams of diethanol amine of addition in four-hole bottle,Amidation process is carried out at a temperature of 95 DEG C~105 DEG C,Amidated products are obtained,It is cooled to 10 DEG C~30 DEG C,65 grams of N are added in most backward four-hole bottle,N- dimethyl sulfoxide (DMSO)s,4 grams of phosphorus pentoxides and 48 grams of phosphoric acid,Heating water bath at 85 DEG C~95 DEG C after esterification is carried out 3 hours,It is cooled to 10 DEG C~30 DEG C,Esterification products are obtained,Dilute with water esterification products,Filtering,Take filter cake,As fluorine-containing demoulding additive is prepared using industrial by-product terpinene.
Embodiment 2
Equipped with agitating device,In the four-hole bottle of reflux condensate device and thermometer,Add 30 grams of terpinenes,1.8 grams of p-methyl benzenesulfonic acid and 1.2 grams of sulfamic acids,After stirring 0.5~1 hour,Add 18 grams of butenoic acids,Being warming up to 150 DEG C~160 DEG C carries out back flow reaction 4 hours,Generation butenoic acid terpinene additive compound,It is cooled to 65~75 DEG C,Add 21 grams of hydrogen peroxide,5.5 grams of glacial acetic acid and 0.6 gram of concentrated sulfuric acid,Carry out epoxidation reaction 3 hours,Generation epoxidation butenoic acid terpinene additive compound,Then it is hydrolyzed with the hot water of 3 times of volumes,Stand,Take oil reservoir,The double hydroxy products of generation,Add 120mL toluene and 110 grams of oligomerization of hexafluoropropylene bodies,Open stirring,It is slowly added to 2 grams of N,N- dimethyl cyclohexyl amines,After nucleophilic substitution being carried out at a temperature of 20 DEG C~35 DEG C 6~8 hours,Distill out toluene,Obtain the product of oligomerization of hexafluoropropylene body substitution,To 27 grams of diethanol amine of addition in four-hole bottle,Amidation process is carried out at a temperature of 85 DEG C~95 DEG C,Amidated products are obtained,It is cooled to 10 DEG C~30 DEG C,80 grams of N are added in most backward four-hole bottle,N- dimethyl sulfoxide (DMSO)s,5 grams of phosphorus pentoxides and 45 grams of phosphoric acid,Heating water bath at 85 DEG C~95 DEG C after esterification is carried out 4 hours,It is cooled to 10 DEG C~30 DEG C,Esterification products are obtained,Dilute with water esterification products,Filtering,Take filter cake,As fluorine-containing demoulding additive is prepared using industrial by-product terpinene.
Embodiment 3
Equipped with agitating device,In the four-hole bottle of reflux condensate device and thermometer,Add 30 grams of terpinenes,1 gram of p-methyl benzenesulfonic acid and 1.5 grams of sulfamic acids,After stirring 0.5~1 hour,Add 24 grams of 2- hexenoic acids,Being warming up to 160 DEG C~170 DEG C carries out back flow reaction 6 hours,Generation hexenoic acid terpinene additive compound,It is cooled to 70~80 DEG C,Add 24 grams of hydrogen peroxide,6.5 grams of glacial acetic acid and 0.7 gram of concentrated sulfuric acid,Carry out epoxidation reaction 5 hours,Generation epoxidation 2- hexenoic acid terpinene additive compounds,Then it is hydrolyzed with the hot water of 3 times of volumes,Stand,Take oil reservoir,The double hydroxy products of generation,Add 100mL toluene and 105 grams of oligomerization of hexafluoropropylene bodies,Open stirring,It is slowly added to 1 gram of N,N- dimethyl cyclohexyl amines,After nucleophilic substitution being carried out at a temperature of 20 DEG C~35 DEG C 6~8 hours,Distill out toluene,Obtain the product of oligomerization of hexafluoropropylene body substitution,To 24 grams of diethanol amine of addition in four-hole bottle,Amidation process is carried out at a temperature of 95 DEG C~105 DEG C,Amidated products are obtained,It is cooled to 10 DEG C~30 DEG C,70 grams of N are added in most backward four-hole bottle,N- dimethyl sulfoxide (DMSO)s,6 grams of phosphorus pentoxides and 42 grams of phosphoric acid,Heating water bath at 85 DEG C~95 DEG C after esterification is carried out 3.5 hours,It is cooled to 10 DEG C~30 DEG C,Esterification products are obtained,Dilute with water esterification products,Filtering,Take filter cake,As fluorine-containing demoulding additive is prepared using industrial by-product terpinene.
The above; implementation method is only that the preferred embodiment of the present invention is described; not the scope of the present invention is defined; on the premise of the spirit for not departing from the technology of the present invention; various modifications and improvement that this area engineers and technicians make to technical scheme, all should fall into the protection domain of claims of the present invention determination.
Claims (2)
1. a kind of method that utilization industrial by-product terpinene prepares fluorine-containing demoulding additive, it is characterized in that：Australene in terpinene, dipentene and terpinolene are isomerizated into α-terpinene, the main component α-terpinene and continuous isomerization in terpinene and come terpinene with（Methyl）Alkenyl acid carries out addition reaction, generation（Methyl）Alkenyl acid terpinene additive compound, epoxidation reaction is carried out with hydrogen peroxide, generates epoxidation（Methyl）Alkenyl acid terpinene additive compound, it is hydrolyzed again, the double hydroxy products of generation, double hydroxy products carry out nucleophilic substitution with oligomerization of hexafluoropropylene body, the product of oligomerization of hexafluoropropylene body substitution is obtained, the product of oligomerization of hexafluoropropylene body substitution carries out amidation process, amidated products are obtained with diethanol amine, finally, amidated products carry out esterification and esterification products are obtained with phosphoric acid；Specifically comprise the steps of：
1) p-methyl benzenesulfonic acid and sulfamic acid effect under, australene, dipentene and terpinolene in terpinene system are isomerizated into α-terpinene, the main component α-terpinene and continuous isomerization in terpinene and come α-terpinene with（Methyl）Alkenyl acid is in back flow reaction 4~6 hours at 150 DEG C~180 DEG C, generation（Methyl）Alkenyl acid terpinene additive compound；
2) under glacial acetic acid and concentrated sulfuric acid effect,（Methyl）Alkenyl acid terpinene additive compound, in epoxidation reaction 4~5 hours at 60~80 DEG C, generates epoxidation with hydrogen peroxide（Methyl）Alkenyl acid terpinene additive compound；
3) epoxidations（Methyl）Alkenyl acid terpinene additive compound, is hydrolyzed with the hot water of 3 times of volumes, is stood, and takes oil reservoir, obtains double hydroxy products；
4) in the presence of N, N- dimethyl cyclohexyl amine, at 20 DEG C~35 DEG C, after double hydroxy products carry out nucleophilic substitution 6~8 hours with oligomerization of hexafluoropropylene body, distills out toluene with toluene as solvent,Obtain the product of oligomerization of hexafluoropropylene body substitution；
5) product and diethanol amine of oligomerization of hexafluoropropylene body substitution, amidation process is carried out at a temperature of 85 DEG C~105 DEG C, and amidated products are obtained, and is cooled to 10 DEG C~30 DEG C；
6) is with N, N- dimethyl sulfoxide (DMSO)s are solvent, in the presence of phosphorus pentoxide, amidated products and phosphoric acid, after heating water bath carries out esterification 3~4 hours in 85 DEG C~95 DEG C, it is cooled to 10 DEG C~30 DEG C, esterification products, dilute with water esterification products, filtering is obtained, filter cake is taken, as fluorine-containing demoulding additive is prepared using industrial by-product terpinene.
2. the method that a kind of utilization industrial by-product terpinene according to claim 1 prepares fluorine-containing demoulding additive, it is characterized in that：Described terpinene,（Methyl）The mass ratio of alkenyl acid, hydrogen peroxide, oligomerization of hexafluoropropylene body, diethanol amine and phosphoric acid is the ﹕ 1.4~1.6 of 1 ﹕, 0.6~0.8 ﹕, 0.7~0.9 ﹕, 3.5~4.0 ﹕ 0.8~1.0；Described p-methyl benzenesulfonic acid and sulfamic acid, its consumption is respectively the 0%~6% of terpinene quality, and its total consumption is the 6%~10% of terpinene quality；Described glacial acetic acid and the concentrated sulfuric acid, its consumption is respectively the 20%~30% and 2%~3% of hydrogen peroxide quality；Described N, N- dimethyl cyclohexyl amine, its consumption are the 3%~5% of terpinene quality.
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Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4554366A (en) * | 1982-09-13 | 1985-11-19 | Shell Oil Company | Certain substituted, 7-oxabicyclo[2.2.1]heptan-2-ols and -2-ones as intermediates |
| CN104672112A (en) * | 2013-11-28 | 2015-06-03 | 修建东 | Method for preparing anti-rust emulsifier by using industrial by-product terpinene |
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2015
- 2015-12-18 CN CN201510948810.4A patent/CN106892941A/en not_active Withdrawn
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4554366A (en) * | 1982-09-13 | 1985-11-19 | Shell Oil Company | Certain substituted, 7-oxabicyclo[2.2.1]heptan-2-ols and -2-ones as intermediates |
| CN104672112A (en) * | 2013-11-28 | 2015-06-03 | 修建东 | Method for preparing anti-rust emulsifier by using industrial by-product terpinene |
Non-Patent Citations (1)
| Title |
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| 王积涛 等: "《有机化学》", 30 September 1997, 南开大学出版社 * |
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