CN115894894A - Petroleum resin emulsifier and preparation method and application thereof - Google Patents
Petroleum resin emulsifier and preparation method and application thereof Download PDFInfo
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- CN115894894A CN115894894A CN202211408022.2A CN202211408022A CN115894894A CN 115894894 A CN115894894 A CN 115894894A CN 202211408022 A CN202211408022 A CN 202211408022A CN 115894894 A CN115894894 A CN 115894894A
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- Prior art keywords
- fatty acid
- oil fatty
- petroleum resin
- anhydride
- acid
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- 239000003208 petroleum Substances 0.000 title claims abstract description 114
- 229920005989 resin Polymers 0.000 title claims abstract description 113
- 239000011347 resin Substances 0.000 title claims abstract description 111
- 239000003995 emulsifying agent Substances 0.000 title claims abstract description 64
- 238000002360 preparation method Methods 0.000 title abstract description 35
- 235000014113 dietary fatty acids Nutrition 0.000 claims abstract description 126
- 239000000194 fatty acid Substances 0.000 claims abstract description 126
- 229930195729 fatty acid Natural products 0.000 claims abstract description 126
- 150000004665 fatty acids Chemical class 0.000 claims abstract description 78
- -1 alcohol amine compound Chemical class 0.000 claims abstract description 76
- 235000015112 vegetable and seed oil Nutrition 0.000 claims abstract description 72
- 239000008158 vegetable oil Substances 0.000 claims abstract description 68
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 52
- 239000000839 emulsion Substances 0.000 claims abstract description 45
- 239000003054 catalyst Substances 0.000 claims abstract description 21
- 229920000642 polymer Polymers 0.000 claims abstract description 13
- 229920005862 polyol Polymers 0.000 claims abstract description 13
- 150000003077 polyols Chemical class 0.000 claims abstract description 13
- 230000002378 acidificating effect Effects 0.000 claims abstract description 10
- 239000002994 raw material Substances 0.000 claims abstract description 10
- 238000006243 chemical reaction Methods 0.000 claims description 46
- 239000013067 intermediate product Substances 0.000 claims description 25
- 239000002253 acid Substances 0.000 claims description 24
- XBDQKXXYIPTUBI-UHFFFAOYSA-N dimethylselenoniopropionate Natural products CCC(O)=O XBDQKXXYIPTUBI-UHFFFAOYSA-N 0.000 claims description 24
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 21
- 229920001223 polyethylene glycol Polymers 0.000 claims description 20
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 18
- 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 16
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 15
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 15
- 239000002202 Polyethylene glycol Substances 0.000 claims description 13
- 235000019260 propionic acid Nutrition 0.000 claims description 12
- IUVKMZGDUIUOCP-BTNSXGMBSA-N quinbolone Chemical compound O([C@H]1CC[C@H]2[C@H]3[C@@H]([C@]4(C=CC(=O)C=C4CC3)C)CC[C@@]21C)C1=CCCC1 IUVKMZGDUIUOCP-BTNSXGMBSA-N 0.000 claims description 12
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 claims description 10
- 239000003377 acid catalyst Substances 0.000 claims description 9
- 238000000034 method Methods 0.000 claims description 9
- AXKGIPZJYUNAIW-UHFFFAOYSA-N (4-aminophenyl)methanol Chemical compound NC1=CC=C(CO)C=C1 AXKGIPZJYUNAIW-UHFFFAOYSA-N 0.000 claims description 8
- HZAXFHJVJLSVMW-UHFFFAOYSA-N 2-Aminoethan-1-ol Chemical compound NCCO HZAXFHJVJLSVMW-UHFFFAOYSA-N 0.000 claims description 8
- 235000019482 Palm oil Nutrition 0.000 claims description 8
- VANNPISTIUFMLH-UHFFFAOYSA-N glutaric anhydride Chemical compound O=C1CCCC(=O)O1 VANNPISTIUFMLH-UHFFFAOYSA-N 0.000 claims description 8
- 239000002540 palm oil Substances 0.000 claims description 8
- FALRKNHUBBKYCC-UHFFFAOYSA-N 2-(chloromethyl)pyridine-3-carbonitrile Chemical compound ClCC1=NC=CC=C1C#N FALRKNHUBBKYCC-UHFFFAOYSA-N 0.000 claims description 7
- 239000003549 soybean oil Substances 0.000 claims description 7
- 235000012424 soybean oil Nutrition 0.000 claims description 7
- 229940014800 succinic anhydride Drugs 0.000 claims description 7
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 claims description 6
- LXQMHOKEXZETKB-UHFFFAOYSA-N 1-amino-2-methylpropan-2-ol Chemical compound CC(C)(O)CN LXQMHOKEXZETKB-UHFFFAOYSA-N 0.000 claims description 4
- JPSKCQCQZUGWNM-UHFFFAOYSA-N 2,7-Oxepanedione Chemical compound O=C1CCCCC(=O)O1 JPSKCQCQZUGWNM-UHFFFAOYSA-N 0.000 claims description 4
- LQGKDMHENBFVRC-UHFFFAOYSA-N 5-aminopentan-1-ol Chemical compound NCCCCCO LQGKDMHENBFVRC-UHFFFAOYSA-N 0.000 claims description 4
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims description 4
- WUGQZFFCHPXWKQ-UHFFFAOYSA-N Propanolamine Chemical compound NCCCO WUGQZFFCHPXWKQ-UHFFFAOYSA-N 0.000 claims description 4
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 4
- 235000019486 Sunflower oil Nutrition 0.000 claims description 4
- 235000019498 Walnut oil Nutrition 0.000 claims description 4
- 239000003240 coconut oil Substances 0.000 claims description 4
- 235000019864 coconut oil Nutrition 0.000 claims description 4
- 239000010460 hemp oil Substances 0.000 claims description 4
- VYFOAVADNIHPTR-UHFFFAOYSA-N isatoic anhydride Chemical compound NC1=CC=CC=C1CO VYFOAVADNIHPTR-UHFFFAOYSA-N 0.000 claims description 4
- 239000003921 oil Substances 0.000 claims description 4
- 235000019198 oils Nutrition 0.000 claims description 4
- 230000035484 reaction time Effects 0.000 claims description 4
- 239000002600 sunflower oil Substances 0.000 claims description 4
- 239000008170 walnut oil Substances 0.000 claims description 4
- AGMZSYQMSHMXLT-UHFFFAOYSA-N 3-aminobutan-1-ol Chemical compound CC(N)CCO AGMZSYQMSHMXLT-UHFFFAOYSA-N 0.000 claims description 3
- HXKKHQJGJAFBHI-UHFFFAOYSA-N 1-aminopropan-2-ol Chemical compound CC(O)CN HXKKHQJGJAFBHI-UHFFFAOYSA-N 0.000 claims description 2
- ZLVLNNCBGQYRAB-UHFFFAOYSA-N 3,3,4,4-tetrafluorooxolane-2,5-dione Chemical compound FC1(F)C(=O)OC(=O)C1(F)F ZLVLNNCBGQYRAB-UHFFFAOYSA-N 0.000 claims description 2
- ACJPFLIEHGFXGP-UHFFFAOYSA-N 3,3-dimethyloxolane-2,5-dione Chemical compound CC1(C)CC(=O)OC1=O ACJPFLIEHGFXGP-UHFFFAOYSA-N 0.000 claims description 2
- NSJAWXMCLJVBPM-UHFFFAOYSA-N 3-butyloxolane-2,5-dione Chemical compound CCCCC1CC(=O)OC1=O NSJAWXMCLJVBPM-UHFFFAOYSA-N 0.000 claims description 2
- YAXXOCZAXKLLCV-UHFFFAOYSA-N 3-dodecyloxolane-2,5-dione Chemical compound CCCCCCCCCCCCC1CC(=O)OC1=O YAXXOCZAXKLLCV-UHFFFAOYSA-N 0.000 claims description 2
- GBBHWGRJHHNAGT-UHFFFAOYSA-N 3-hexadecyloxolane-2,5-dione Chemical compound CCCCCCCCCCCCCCCCC1CC(=O)OC1=O GBBHWGRJHHNAGT-UHFFFAOYSA-N 0.000 claims description 2
- DFATXMYLKPCSCX-UHFFFAOYSA-N 3-methylsuccinic anhydride Chemical compound CC1CC(=O)OC1=O DFATXMYLKPCSCX-UHFFFAOYSA-N 0.000 claims description 2
- ZJFCVUTYZHUNSW-UHFFFAOYSA-N 3-octadecyloxolane-2,5-dione Chemical compound CCCCCCCCCCCCCCCCCCC1CC(=O)OC1=O ZJFCVUTYZHUNSW-UHFFFAOYSA-N 0.000 claims description 2
- OAJCSERLBQROJC-UHFFFAOYSA-N 3-octyloxolane-2,5-dione Chemical compound CCCCCCCCC1CC(=O)OC1=O OAJCSERLBQROJC-UHFFFAOYSA-N 0.000 claims description 2
- BZECBEKZECEQRI-UHFFFAOYSA-N 3-tetradecyloxolane-2,5-dione Chemical compound CCCCCCCCCCCCCCC1CC(=O)OC1=O BZECBEKZECEQRI-UHFFFAOYSA-N 0.000 claims description 2
- 240000001548 Camellia japonica Species 0.000 claims description 2
- 241001655736 Catalpa bignonioides Species 0.000 claims description 2
- 244000170916 Paeonia officinalis Species 0.000 claims description 2
- 235000006484 Paeonia officinalis Nutrition 0.000 claims description 2
- 235000019483 Peanut oil Nutrition 0.000 claims description 2
- 235000004347 Perilla Nutrition 0.000 claims description 2
- 244000124853 Perilla frutescens Species 0.000 claims description 2
- 235000019774 Rice Bran oil Nutrition 0.000 claims description 2
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims description 2
- 239000004359 castor oil Substances 0.000 claims description 2
- 235000019438 castor oil Nutrition 0.000 claims description 2
- 235000018597 common camellia Nutrition 0.000 claims description 2
- 239000002285 corn oil Substances 0.000 claims description 2
- 235000005687 corn oil Nutrition 0.000 claims description 2
- 235000012343 cottonseed oil Nutrition 0.000 claims description 2
- 239000002385 cottonseed oil Substances 0.000 claims description 2
- ZEMPKEQAKRGZGQ-XOQCFJPHSA-N glycerol triricinoleate Natural products CCCCCC[C@@H](O)CC=CCCCCCCCC(=O)OC[C@@H](COC(=O)CCCCCCCC=CC[C@@H](O)CCCCCC)OC(=O)CCCCCCCC=CC[C@H](O)CCCCCC ZEMPKEQAKRGZGQ-XOQCFJPHSA-N 0.000 claims description 2
- 229940102253 isopropanolamine Drugs 0.000 claims description 2
- 239000000944 linseed oil Substances 0.000 claims description 2
- 235000021388 linseed oil Nutrition 0.000 claims description 2
- 239000010507 melon oil Substances 0.000 claims description 2
- 239000004006 olive oil Substances 0.000 claims description 2
- 235000008390 olive oil Nutrition 0.000 claims description 2
- 239000000312 peanut oil Substances 0.000 claims description 2
- 230000008569 process Effects 0.000 claims description 2
- 239000008165 rice bran oil Substances 0.000 claims description 2
- 239000008159 sesame oil Substances 0.000 claims description 2
- 235000011803 sesame oil Nutrition 0.000 claims description 2
- 239000002383 tung oil Substances 0.000 claims description 2
- 150000001875 compounds Chemical class 0.000 claims 1
- 238000004519 manufacturing process Methods 0.000 abstract description 7
- 239000007787 solid Substances 0.000 abstract description 4
- 238000009776 industrial production Methods 0.000 abstract description 2
- 238000010438 heat treatment Methods 0.000 description 42
- 238000010992 reflux Methods 0.000 description 38
- 238000003756 stirring Methods 0.000 description 33
- 230000000740 bleeding effect Effects 0.000 description 23
- 238000009833 condensation Methods 0.000 description 14
- 230000005494 condensation Effects 0.000 description 14
- 238000004821 distillation Methods 0.000 description 14
- 239000002904 solvent Substances 0.000 description 13
- 239000000047 product Substances 0.000 description 12
- 230000000052 comparative effect Effects 0.000 description 10
- 238000005917 acylation reaction Methods 0.000 description 9
- 239000002245 particle Substances 0.000 description 8
- 238000003860 storage Methods 0.000 description 7
- 238000005406 washing Methods 0.000 description 7
- 239000000853 adhesive Substances 0.000 description 6
- 230000001070 adhesive effect Effects 0.000 description 6
- WBIQQQGBSDOWNP-UHFFFAOYSA-N 2-dodecylbenzenesulfonic acid Chemical compound CCCCCCCCCCCCC1=CC=CC=C1S(O)(=O)=O WBIQQQGBSDOWNP-UHFFFAOYSA-N 0.000 description 5
- 229940060296 dodecylbenzenesulfonic acid Drugs 0.000 description 5
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- 238000012360 testing method Methods 0.000 description 4
- 239000003513 alkali Substances 0.000 description 3
- 238000001816 cooling Methods 0.000 description 3
- 238000004945 emulsification Methods 0.000 description 3
- 230000001804 emulsifying effect Effects 0.000 description 3
- 230000032050 esterification Effects 0.000 description 3
- 238000005886 esterification reaction Methods 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 239000003973 paint Substances 0.000 description 3
- 239000002518 antifoaming agent Substances 0.000 description 2
- 238000000576 coating method Methods 0.000 description 2
- 238000006297 dehydration reaction Methods 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 238000002844 melting Methods 0.000 description 2
- 238000001556 precipitation Methods 0.000 description 2
- 239000008213 purified water Substances 0.000 description 2
- 238000010998 test method Methods 0.000 description 2
- 239000004820 Pressure-sensitive adhesive Substances 0.000 description 1
- GSEJCLTVZPLZKY-UHFFFAOYSA-N Triethanolamine Chemical compound OCCN(CCO)CCO GSEJCLTVZPLZKY-UHFFFAOYSA-N 0.000 description 1
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 1
- 125000003368 amide group Chemical group 0.000 description 1
- 150000001408 amides Chemical class 0.000 description 1
- 239000002585 base Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- VEFXTGTZJOWDOF-UHFFFAOYSA-N benzene;hydrate Chemical compound O.C1=CC=CC=C1 VEFXTGTZJOWDOF-UHFFFAOYSA-N 0.000 description 1
- 239000011203 carbon fibre reinforced carbon Substances 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000006482 condensation reaction Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 230000018044 dehydration Effects 0.000 description 1
- 238000010790 dilution Methods 0.000 description 1
- 239000012895 dilution Substances 0.000 description 1
- 238000007599 discharging Methods 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- GVGUFUZHNYFZLC-UHFFFAOYSA-N dodecyl benzenesulfonate;sodium Chemical compound [Na].CCCCCCCCCCCCOS(=O)(=O)C1=CC=CC=C1 GVGUFUZHNYFZLC-UHFFFAOYSA-N 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 150000002191 fatty alcohols Chemical class 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- PSZYNBSKGUBXEH-UHFFFAOYSA-N naphthalene-1-sulfonic acid Chemical class C1=CC=C2C(S(=O)(=O)O)=CC=CC2=C1 PSZYNBSKGUBXEH-UHFFFAOYSA-N 0.000 description 1
- ZPIRTVJRHUMMOI-UHFFFAOYSA-N octoxybenzene Chemical compound CCCCCCCCOC1=CC=CC=C1 ZPIRTVJRHUMMOI-UHFFFAOYSA-N 0.000 description 1
- 238000005120 petroleum cracking Methods 0.000 description 1
- 229920000056 polyoxyethylene ether Polymers 0.000 description 1
- 229940080264 sodium dodecylbenzenesulfonate Drugs 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 238000003892 spreading Methods 0.000 description 1
- 230000007480 spreading Effects 0.000 description 1
- 229920001909 styrene-acrylic polymer Polymers 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 229920001169 thermoplastic Polymers 0.000 description 1
- 239000004416 thermosoftening plastic Substances 0.000 description 1
Landscapes
- Emulsifying, Dispersing, Foam-Producing Or Wetting Agents (AREA)
Abstract
The invention provides a petroleum resin emulsifier and a preparation method and application thereof, wherein the preparation raw materials of the petroleum resin emulsifier comprise vegetable oil fatty acid, monohydric alcohol, acidic catalyst, alkaline catalyst, alcohol amine compound, cyclic anhydride and polymer polyol; by selecting renewable vegetable oil fatty acid and other components as preparation raw materials of the petroleum resin emulsifier, when the waterborne petroleum resin emulsion is prepared, the waterborne petroleum resin emulsion with higher solid content can be obtained under the condition of lower addition amount, and the stability of the waterborne petroleum resin emulsion can be effectively improved, so that the production cost of the waterborne petroleum resin emulsion is effectively reduced, and the waterborne petroleum resin emulsion is suitable for batch industrial production.
Description
Technical Field
The invention belongs to the technical field of emulsifiers, and particularly relates to a petroleum resin emulsifier, and a preparation method and application thereof.
Background
The petroleum resin is a thermoplastic oligomer resin with the molecular weight of 300-3000 synthesized by petroleum cracking products, has the characteristics of low acid value, water resistance, ethanol resistance, chemical resistance and the like, and has the characteristics of good chemical stability and thermal stability to acid and alkali, so that the petroleum resin is widely applied to various industries and fields such as rubber, adhesives, coatings, papermaking, printing ink and the like in recent years, can increase the glossiness of paint, and improves the adhesive force, hardness, acid resistance and alkali resistance of a paint film; the color spreading, quick drying, glossiness and printing performance of the ink are improved; the paint for road marking and line drawing can also improve the excellent adhesive force, and has the advantages of good wear resistance and water resistance, good weather resistance, fast drying, high firmness and the like.
The petroleum resin also has good adhesion, and the addition of the petroleum resin to the adhesive and the pressure-sensitive adhesive tape can improve the adhesive force, acid resistance, alkali resistance and water resistance of the adhesive and can effectively reduce the production cost. However, petroleum resins cannot be used directly in aqueous systems, and therefore petroleum resins are generally used in production by being prepared into aqueous emulsions.
Conventional emulsifiers used in the manufacture of aqueous petroleum resin emulsions include dodecylbenzene sulfonic acid, fatty alcohol polyoxyethylene ethers, naphthalene sulfonates, and the like. CN100564445A discloses a petroleum resin emulsion, which comprises petroleum resin, petroleum ether, polyethylene glycol octyl phenyl ether, sodium dodecyl benzene sulfonate, water and a defoaming agent. Adding petroleum resin, petroleum ether and an emulsifier into a reaction container according to the amount, and heating and stirring; when the system is in a full-melting state, slowly heating to a certain temperature, stopping heating, naturally cooling, dispersing in cold water, adding a defoaming agent, and discharging. The petroleum resin emulsion is used for preparing exterior wall coating by taking the petroleum resin emulsion and styrene-acrylic emulsion or pure acrylic emulsion as base materials; the preparation method of the emulsion has the advantages of simultaneous dissolution and emulsification of the petroleum resin, simple operation, short process flow, complete emulsification reaction, environment-friendly emulsifier, high preparation rate and good product stability. However, the emulsifier in the prior art is large in addition amount, difficult to emulsify and high in energy consumption, and the obtained emulsion petroleum resin is low in solid content, short in stability period and difficult to store for a long time, so that the production cost is directly or indirectly overhigh.
Therefore, the development of a petroleum resin emulsifier with good emulsifying effect and low addition amount is a technical problem which needs to be solved urgently in the field.
Disclosure of Invention
Aiming at the defects of the prior art, the invention aims to provide a petroleum resin emulsifier, a preparation method and application thereof, wherein the petroleum resin emulsifier takes vegetable oil fatty acid as one of preparation raw materials, has excellent emulsification effect, can obtain high-solid aqueous petroleum resin emulsion under the condition of small addition amount in an emulsion system, and can also effectively improve the stability of the aqueous petroleum resin emulsion.
In order to achieve the purpose, the invention adopts the following technical scheme:
in a first aspect, the present invention provides a petroleum resin emulsifier, which is prepared from a raw material comprising a combination of vegetable oil fatty acid, monohydric alcohol, acidic catalyst, basic catalyst, alcohol amine compound, cyclic acid anhydride and polymer polyol.
The preparation raw materials of the petroleum resin emulsifier provided by the invention comprise vegetable oil fatty acid, monohydric alcohol, an acidic catalyst, a basic catalyst, an alcohol amine compound, cyclic anhydride and polymer polyol, and the efficient emulsifier prepared by selecting the preparation raw materials in a matching way not only has an excellent emulsifying effect, but also can obtain a high-solid-content aqueous petroleum resin emulsion under the condition of lower addition amount in an emulsion system, and the obtained aqueous petroleum resin emulsion has excellent stability, so that the production cost of an enterprise is effectively reduced.
Preferably, the vegetable oil fatty acid includes any one or a combination of at least two of tung oil fatty acid, catalpa oil fatty acid, linseed oil fatty acid, perilla oil fatty acid, hemp oil fatty acid, soybean oil fatty acid, sunflower oil fatty acid, cottonseed oil fatty acid, corn oil fatty acid, coconut oil fatty acid, rice bran oil fatty acid, sesame oil fatty acid, castor oil fatty acid, peanut oil fatty acid, melon seed oil fatty acid, camellia seed oil fatty acid, peony seed oil fatty acid, palm oil fatty acid, walnut oil fatty acid, or olive oil fatty acid, and further preferably any one or a combination of at least two of palm oil fatty acid, coconut oil fatty acid, soybean oil fatty acid, hemp oil fatty acid, sunflower oil fatty acid, or walnut oil fatty acid.
Preferably, the monohydric alcohol comprises any one of methanol, ethanol, n-propanol or isopropanol or a combination of at least two thereof, further preferably methanol and/or ethanol.
Preferably, the molar ratio of the vegetable oil fatty acid to the monohydric alcohol is 1 (2-8), such as 1.
Preferably, the acidic catalyst comprises any one of sulfuric acid, p-toluenesulfonic acid, phosphoric acid or propionic acid, or a combination of at least two thereof.
Preferably, the basic catalyst comprises sodium hydroxide and/or potassium hydroxide.
Preferably, the amide compound includes any one or a combination of at least two of isopropanolamine, ethanolamine, DL-aminopropanol, propanolamine, 1-amino-2-methyl-2-propanol, 3-aminon-butanol, 5-amino-1-pentanol, p-aminobenzyl alcohol, 2-aminobenzyl alcohol or 4-aminobenzyl alcohol, and further preferably p-aminobenzyl alcohol and/or 5-amino-1-pentanol.
Preferably, the cyclic anhydride includes any one or a combination of at least two of succinic anhydride, adipic anhydride, glutaric anhydride, tetrafluorosuccinic anhydride, butylsuccinic anhydride, 2-methylsuccinic anhydride, n-octylsuccinic anhydride, dodecylsuccinic anhydride, tetradecylsuccinic anhydride, hexadecylsuccinic anhydride, octadecylsuccinic anhydride, or 2,2-dimethylsuccinic anhydride, and further preferably any one or a combination of at least two of succinic anhydride, glutaric anhydride, or adipic anhydride.
Preferably, the polymer polyol comprises polyethylene glycol.
Preferably, the polyethylene glycol has a molar mass of 600 to 6000g/mol, for example 1000g/mol, 1500g/mol, 2000g/mol, 2500g/mol, 3000g/mol, 3500g/mol, 4000g/mol, 4500g/mol, 5000g/mol or 5500g/mol, and more preferably 1000 to 2500g/mol.
In a second aspect, the present invention provides a method for preparing the petroleum resin emulsifier according to the first aspect, the method comprising the steps of:
(1) Reacting vegetable oil fatty acid with monohydric alcohol under the condition of an acid catalyst to obtain vegetable oil fatty acid ester;
(2) Reacting the vegetable oil fatty acid ester obtained in the step (1) with an alcohol amine compound under the condition of an alkaline catalyst to obtain vegetable oil fatty acid alcohol amide;
(3) Reacting the vegetable oil fatty acid alcohol amide obtained in the step (2) with cyclic acid anhydride to obtain an intermediate product;
(4) And (4) reacting the intermediate product obtained in the step (3) with polymer polyol under an acidic condition to obtain the petroleum resin emulsifier.
In the preparation method provided by the invention, in the step (1), vegetable oil fatty acid ester is obtained by carrying out esterification and dehydration reaction on vegetable oil fatty acid and monohydric alcohol under the condition of an acid catalyst; then, in the step (2), the obtained vegetable oil fatty acid and alcohol amine compound are subjected to acylation reaction under the condition of an alkaline catalyst to obtain vegetable oil fatty acid alcohol amide; reacting the obtained vegetable oil amide with cyclic acid anhydride (without carbon-carbon double bonds), and respectively carrying out esterification and acylation reactions by utilizing hydroxyl, amido and the cyclic acid anhydride to obtain an intermediate product containing dicarboxyl; and (4) performing dehydration, esterification and condensation reaction on the obtained intermediate product containing the dicarboxyl and polymer polyol under the condition of an acid catalyst to obtain the petroleum resin emulsifier.
Preferably, the temperature of the reaction in step (1) is 50 to 100 ℃, such as 55 ℃, 60 ℃, 65 ℃, 70 ℃, 75 ℃, 80 ℃, 85 ℃, 90 ℃ or 95 ℃.
Preferably, the reaction in step (1) is terminated at an acid value of the system of not higher than 5mgKOH/g (e.g., 4.5mgKOH/g, 4mgKOH/g, 3.5mgKOH/g, 3mgKOH/g, 2.5mgKOH/g, 2mgKOH/g, or 1.5 mgKOH/g).
Preferably, the mass of the acid catalyst in step (1) is 0.5 to 2%, for example, 0.7%, 0.9%, 1.1%, 1.3%, 1.5%, 1.7%, 1.9%, or the like, based on 100% of the mass of the vegetable oil fatty acid.
Preferably, the temperature of the reaction in step (2) is 120 to 160 ℃, such as 125 ℃, 130 ℃, 135 ℃, 140 ℃, 145 ℃, 150 ℃, or 155 ℃ and the like.
Preferably, the reaction time in step (2) is 3 to 5 hours, such as 3.2 hours, 3.4 hours, 3.6 hours, 3.8 hours, 4 hours, 4.2 hours, 4.4 hours, 4.6 hours, or 4.8 hours, etc.
Preferably, in the step (2), the molar ratio of the vegetable oil fatty acid ester to the alcohol amine compound is 1 (1 to 1.5), such as 1.
Preferably, the amount of the basic catalyst in the step (2) is 0.5 to 2% by mass, for example, 0.7%, 0.9%, 1.1%, 1.3%, 1.5%, 1.7%, 1.9%, or the like, based on 100% by mass of the vegetable oil fatty acid ester.
Preferably, the temperature of the reaction in step (3) is 120 to 180 ℃, such as 130 ℃, 140 ℃, 150 ℃, 160 ℃, or 170 ℃, and the like.
Preferably, the reaction time in step (3) is 3 to 5 hours, such as 3.3 hours, 3.6 hours, 3.9 hours, 4.2 hours, 4.5 hours, or 4.8 hours, etc.
Preferably, the mass ratio of the vegetable oil fatty acid alcohol amide to the cyclic anhydride in step (3) is 1 (0.5 to 1.5), such as 1.
Preferably, the molar ratio of the polymer polyol and the intermediate product in step (4) is (1-2): 1, e.g. 1.2.
Preferably, the temperature of the reaction in step (4) is 150 to 220 ℃, such as 160 ℃, 170 ℃, 180 ℃, 190 ℃, 200 ℃ or 210 ℃, etc.
Preferably, the reaction in step (4) is terminated at an acid value of not higher than 5mgKOH/g (e.g., 4.5mgKOH/g, 4mgKOH/g, 3.5mgKOH/g, 3mgKOH/g, 2.5mgKOH/g, 2mgKOH/g, or 1.5 mgKOH/g).
Preferably, the mass of the acidic catalyst in step (4) is 0.5 to 2%, for example, 0.7%, 0.9%, 1.1%, 1.3%, 1.5%, 1.7%, 1.9%, or the like, based on 100% of the mass of the intermediate product.
As a preferred technical scheme of the invention, the preparation method comprises the following steps:
(1) Vegetable oil fatty acid, monohydric alcohol and acid catalyst react at 50-100 ℃ until the acid value of the system is not higher than 5mgKOH/g, and vegetable oil fatty acid ester is obtained;
(2) Reacting the vegetable oil fatty acid ester obtained in the step (1), alcohol amine compound and alkaline catalyst at 120-160 ℃ for 3-5 h to obtain vegetable oil fatty acid alcohol amide;
(3) Reacting the vegetable oil fatty acid alcohol amide obtained in the step (2) with cyclic acid anhydride at 120-180 ℃ for 3-5 h to obtain an intermediate product;
(4) And (4) reacting the intermediate product obtained in the step (3), polymer polyol and an acid catalyst at the temperature of 150-220 ℃ until the acid value of the system is not higher than 5mgKOH/g, thus obtaining the petroleum resin emulsifier.
In a third aspect, the present invention provides an aqueous petroleum resin emulsion comprising the petroleum resin emulsifier of the first aspect.
Compared with the prior art, the invention has the following beneficial effects:
the raw materials for preparing the petroleum resin emulsifier comprise vegetable oil fatty acid, monohydric alcohol, an acidic catalyst, a basic catalyst, an alcohol amine compound, cyclic acid anhydride and polymer polyol; by selecting renewable vegetable oil fatty acid and other components as preparation raw materials of the petroleum resin emulsifier, when the waterborne petroleum resin emulsion is prepared, the waterborne petroleum resin emulsion with higher solid content can be obtained under the condition of lower addition amount, and the stability of the waterborne petroleum resin emulsion can be effectively improved, so that the production cost of the waterborne petroleum resin emulsion is effectively reduced, and the waterborne petroleum resin emulsion is suitable for batch industrial production.
Detailed Description
The technical solution of the present invention is further described below by way of specific embodiments. It should be understood by those skilled in the art that the examples are only for the understanding of the present invention and should not be construed as the specific limitations of the present invention.
Example 1
The preparation method of the petroleum resin emulsifier comprises the following steps:
(1) Adding 500g of palm oil fatty acid, 500g of ethanol and 5g of propionic acid into a reaction vessel with stirring, refluxing and heating functions, stirring and heating to 78 ℃, reacting in a condensation reflux state until the acid value is not higher than 5mgKOH/g, carrying out reduced pressure distillation to collect unreacted ethanol, washing a product with pure water, and carrying out reduced pressure distillation to obtain vegetable oil fatty acid ester;
(2) Adding 300g of the vegetable oil fatty acid ester obtained in the step (1), 74g of ethanolamine and 3g of potassium hydroxide into a reaction vessel with stirring, refluxing and heating functions, heating to 140 ℃ for acylation reaction, and continuously removing the solvent by condensation and refluxing until no obvious substances are evaporated to stop the reaction to obtain vegetable oil fatty acid alcohol amide;
(3) Adding 300g of vegetable oil fatty acid alcohol amide obtained in the step (2) and 192g of succinic anhydride into a reaction vessel with stirring, refluxing and heating functions, and reacting for 4 hours at 160 ℃ to obtain an intermediate product;
(4) Adding 2550g of polyethylene glycol (PEG 2000) and 30g of propionic acid into the intermediate product obtained in the step (3), and reacting at 160 ℃ until the acid value of the system is not higher than 5mgKOH/g to obtain the petroleum resin emulsifier.
Example 2
The preparation method of the petroleum resin emulsifier comprises the following steps:
(1) Adding 500g of soybean oil fatty acid, 440g of isopropanol and 5g of p-toluenesulfonic acid into a reaction vessel with stirring, refluxing and heating, stirring and heating to 83 ℃, reacting under a condensation reflux state until the acid value is not higher than 5mgKOH/g, carrying out reduced pressure distillation to collect unreacted ethanol, washing a product with pure water, and carrying out reduced pressure distillation to obtain vegetable oil fatty acid ester;
(2) Adding 350g of vegetable oil fatty acid ester obtained in the step (1), 152g of p-aminobenzyl alcohol and 3.5g of sodium hydroxide into a reaction vessel with stirring, refluxing and heating, heating to 155 ℃ for acylation reaction, and continuously removing the solvent by condensation and refluxing until no solvent is evaporated to stop the reaction to obtain vegetable oil fatty acid alcohol amide;
(3) Adding 300g of vegetable oil fatty acid alcohol amide obtained in the step (2) and 209g of glutaric anhydride into a reaction vessel with stirring, refluxing and heating functions, and reacting for 4 hours at 140 ℃ to obtain an intermediate product;
(4) Adding 2000g of polyethylene glycol (PEG 2000) and 37g of p-toluenesulfonic acid into the intermediate product obtained in the step (3), and reacting at 190 ℃ until the acid value of the system is not higher than 5mgKOH/g to obtain the petroleum resin emulsifier.
Example 3
The preparation method of the petroleum resin emulsifier comprises the following steps:
(1) Adding 500g of palm oil fatty acid, 500g of ethanol and 5g of propionic acid into a reaction vessel with stirring, refluxing and heating functions, stirring and heating to 78 ℃, reacting in a condensation reflux state until the acid value is not higher than 5mgKOH/g, carrying out reduced pressure distillation to collect unreacted ethanol, washing a product with pure water, and carrying out reduced pressure distillation to obtain vegetable oil fatty acid ester;
(2) Adding 300g of the vegetable oil fatty acid ester obtained in the step (1), 98g of propanolamine and 3g of potassium hydroxide into a reaction vessel with stirring, refluxing and heating, heating to 145 ℃ for acylation reaction, and continuously removing the solvent by condensation and refluxing until no solvent is evaporated to stop the reaction to obtain vegetable oil fatty acid alcohol amide;
(3) Adding 300g of vegetable oil fatty acid alcohol amide obtained in the step (2) and 209g of glutaric anhydride into a reaction vessel with stirring, refluxing and heating functions, and reacting for 4 hours at 160 ℃ to obtain an intermediate product;
(4) Adding 2750g of polyethylene glycol (PEG 2500) and 39g of propionic acid into the intermediate product obtained in the step (3), and reacting at 200 ℃ until the acid value of the system is not higher than 5mgKOH/g to obtain the petroleum resin emulsifier.
Example 4
The preparation method of the petroleum resin emulsifier comprises the following steps:
(1) Adding 500g of soybean oil fatty acid, 440g of isopropanol and 5g of p-toluenesulfonic acid into a reaction vessel with stirring, refluxing and heating, stirring and heating to 83 ℃, reacting under a condensation reflux state until the acid value is not higher than 5mgKOH/g, carrying out reduced pressure distillation to collect unreacted ethanol, washing a product with pure water, and carrying out reduced pressure distillation to obtain vegetable oil fatty acid ester;
(2) Adding 350g of the vegetable oil fatty acid ester obtained in the step (1), 118g of 3-amino n-butanol and 3.5g of sodium hydroxide into a reaction vessel with stirring, refluxing and heating functions, heating to 155 ℃ for acylation reaction, and continuously removing the solvent by condensation and refluxing until no solvent is evaporated to stop the reaction to obtain vegetable oil fatty acid alcohol amide;
(3) Adding 300g of the vegetable oil fatty acid alcohol amide obtained in the step (2) and 176g of succinic anhydride into a reaction vessel with stirring, refluxing and heating functions, and reacting for 4 hours at 140 ℃ to obtain an intermediate product;
(4) Adding 2500g of polyethylene glycol (PEG 2000) and 37g of p-toluenesulfonic acid into the intermediate product obtained in the step (3), and reacting at 190 ℃ until the acid value of the system is not higher than 5mgKOH/g to obtain the petroleum resin emulsifier.
Example 5
The preparation method of the petroleum resin emulsifier comprises the following steps:
(1) Adding 500g of palm oil fatty acid, 500g of ethanol and 5g of propionic acid into a reaction vessel with stirring, refluxing and heating functions, stirring and heating to 78 ℃, reacting under a condensation reflux state until the acid value is not higher than 5mgKOH/g, carrying out reduced pressure distillation to collect unreacted ethanol, washing a product with pure water, and carrying out reduced pressure distillation to obtain vegetable oil fatty acid ester;
(2) Adding 300g of the vegetable oil fatty acid ester obtained in the step (1), 98g of propanolamine and 3g of potassium hydroxide into a reaction vessel with stirring, refluxing and heating, heating to 145 ℃ for acylation reaction, and continuously removing the solvent by condensation and refluxing until no solvent is evaporated to stop the reaction to obtain vegetable oil fatty acid alcohol amide;
(3) Adding 300g of vegetable oil fatty acid alcohol amide obtained in the step (2) and 209g of glutaric anhydride into a reaction vessel with stirring, refluxing and heating functions, and reacting for 4 hours at 160 ℃ to obtain an intermediate product;
(4) And (3) adding 300g of the intermediate product obtained in the step (3), 950g of polyethylene glycol (PEG 150) and 15g of propionic acid into a reaction vessel with stirring, refluxing and heating, and reacting at 170 ℃ until the acid value of the system is not higher than 5mgKOH/g to obtain the petroleum resin emulsifier.
Example 6
A petroleum resin emulsifier which is different from example 5 in that the addition amount of polyethylene glycol in step (4) is 920g, 14g of p-toluenesulfonic acid is used in place of 15g of propionic acid, the reaction temperature is adjusted to 160 ℃, and other substances, amounts and conditions are the same as in example 5.
Example 7
The preparation method of the petroleum resin emulsifier comprises the following steps:
(1) Adding 500g of palm oil fatty acid, 500g of ethanol and 5g of propionic acid into a reaction vessel with stirring, refluxing and heating functions, stirring and heating to 78 ℃, reacting in a condensation reflux state until the acid value is not higher than 5mgKOH/g, carrying out reduced pressure distillation to collect unreacted ethanol, washing a product with pure water, and carrying out reduced pressure distillation to obtain vegetable oil fatty acid ester;
(2) Adding 300g of the vegetable oil fatty acid ester obtained in the step (1), 74g of ethanolamine and 3g of potassium hydroxide into a reaction vessel with stirring, refluxing and heating functions, heating to 140 ℃ for acylation reaction, and continuously removing the solvent by condensation and refluxing until no solvent is evaporated to stop the reaction to obtain vegetable oil fatty acid alcohol amide;
(3) Adding 300g of vegetable oil fatty acid alcohol amide obtained in the step (2) and 192g of succinic anhydride into a reaction vessel with stirring, refluxing and heating functions, and reacting for 4 hours at 160 ℃ to obtain an intermediate product;
(4) And (3) adding 300g of the intermediate product obtained in the step (3), 1600g of polyethylene glycol (PEG 2500) and 19g of propionic acid into a reaction vessel with stirring, refluxing and heating, and reacting at 200 ℃ until the acid value of the system is not higher than 5mgKOH/g to obtain the petroleum resin emulsifier.
Example 8
The preparation method of the petroleum resin emulsifier comprises the following steps:
(1) Adding 500g of soybean oil fatty acid, 440g of isopropanol and 5g of p-toluenesulfonic acid into a reaction vessel with stirring, refluxing and heating functions, stirring and heating to 83 ℃, reacting under a condensation reflux state until the acid value is not higher than 5mgKOH/g, carrying out reduced pressure distillation to collect unreacted ethanol, washing a product with pure water, and carrying out reduced pressure distillation to obtain vegetable oil fatty acid ester;
(2) Adding 350g of vegetable oil fatty acid ester obtained in the step (1), 152g of p-aminobenzyl alcohol and 3.5g of sodium hydroxide into a reaction vessel with stirring, refluxing and heating, heating to 155 ℃ for acylation reaction, and continuously removing the solvent by condensation and refluxing until no solvent is evaporated to stop the reaction to obtain vegetable oil fatty acid alcohol amide;
(3) Adding 300g of vegetable oil fatty acid alcohol amide obtained in the step (2) and 209g of glutaric anhydride into a reaction vessel with stirring, refluxing and heating functions, and reacting for 4 hours at 140 ℃ to obtain an intermediate product;
(4) And (3) adding 300g of the intermediate product obtained in the step (3), 1400g of polyethylene glycol (PEG 2500) and 15g of propionic acid into a reaction vessel with stirring, refluxing and heating, and reacting at 210 ℃ until the acid value of the system is not higher than 5mgKOH/g to obtain the petroleum resin emulsifier.
Example 9
A petroleum resin emulsifier which differs from example 1 only in that ethanol is replaced with an equimolar amount of methanol, and other materials, amounts and preparation methods are the same as example 1.
Example 10
A petroleum resin emulsifier which differs from example 1 only in that ethanol is replaced by n-propanol in an equimolar amount, and the other materials, amounts and preparation methods are the same as example 1.
Application example 1
The preparation method of the water-based petroleum resin emulsion comprises the following components in parts by weight:
the preparation method of the aqueous petroleum resin emulsion provided by the application example comprises the following steps: adding C5 petroleum resin (Puyang Kerneteder petroleum resin Co., ltd., BT-A1100) into an emulsifying flask with a thermometer and an electric stirrer, heating to 130 ℃ for melting, adding a petroleum resin emulsifier (example 1) and triethanolamine, stirring at 1150rpm, starting cooling to 100 ℃, slowly adding purified water with the temperature of more than 90 ℃ into the flask in batches for phase inversion, adding purified water at room temperature for dilution after the phase inversion is finished, cooling to room temperature, and filtering to obtain the aqueous petroleum resin emulsion.
Application examples 2 to 10
An aqueous petroleum resin emulsion which differs from application example 1 only in that the petroleum resin emulsifier obtained in example 1 was replaced with the petroleum resin emulsifier obtained in examples 2 to 10, respectively, and the other components, amounts and preparation methods were the same as in application example 1.
Application example 11
The preparation method of the water-based petroleum resin emulsion comprises the following components in parts by weight:
wherein the C9 petroleum resin is from Puyang Kerred petroleum resin Co., ltd, BT-F1100, and the petroleum resin emulsifier is from example 1;
the preparation method of the petroleum resin emulsion provided in the application example is the same as that of application example 1.
Application examples 12 to 20
An aqueous petroleum resin emulsion which differs from application example 11 only in that the petroleum resin emulsifier obtained in example 1 was replaced with the petroleum resin emulsifier obtained in examples 2 to 10, respectively, and the other components, amounts and preparation methods were the same as in application example 11.
Comparative application example 1
An aqueous petroleum resin emulsion which differs from application example 1 only in that dodecylbenzene sulfonic acid was used instead of the petroleum resin emulsifier obtained in example 1, and the other components, amounts and preparation methods were the same as in application example 1.
Comparative application example 2
An aqueous petroleum resin emulsion which differs from application example 1 only in that the petroleum resin emulsifier obtained in example 1 was replaced with OP-10, and the other components, amounts and preparation methods were the same as in application example 1.
Comparative application example 3
An aqueous petroleum resin emulsion which is different from application example 11 only in that dodecylbenzene sulfonic acid is used instead of the petroleum resin emulsifier obtained in example 1, and other components, amounts and preparation methods are the same as application example 11.
Comparative application example 4
An aqueous petroleum resin emulsion which is different from application example 11 only in that the petroleum resin emulsifier obtained in example 1 is replaced by OP-10, and other components, the amount and the preparation method are the same as those of application example 11.
And (3) performance testing:
(1) Appearance: visually observing the color of the aqueous petroleum resin emulsion;
(2) Average particle size: testing by using a Dandongbeit BT-90 laser particle size analyzer;
(3) Storage stability: the storage was carried out at 55 ℃ for 14d, and the change in appearance was observed.
The aqueous petroleum resin emulsions obtained in application examples 1 to 10 and comparative application examples 1 to 2 were tested according to the above test method, and the test results are shown in table 1:
TABLE 1
| Appearance of the product | Average particle diameter/nm | Storage stability | |
| Application example 1 | White colour | 432 | No crusting and no bleeding |
| Application example 2 | White colour | 389 | No crusting and no bleeding |
| Application example 3 | White colour | 299 | Without crusting and bleeding |
| Application example 4 | White colour | 415 | No crusting and no bleeding |
| Application example 5 | White colour | 376 | Without crusting and bleeding |
| Application example 6 | White colour | 325 | No crusting and no bleeding |
| Application example 7 | White colour | 335 | No crusting and no bleeding |
| Application example 8 | White colour | 478 | No crusting and no bleeding |
| Application example 9 | White colour | 525 | Without crusting and bleeding |
| Application example 10 | White colour | 435 | No crusting and no bleeding |
| Comparative application example 1 | White colour | 1235 | No precipitation of water and crust |
| Comparative application example 2 | White colour | 1438 | No precipitation of water and crust |
According to the data in table 1, the C5 aqueous petroleum resin emulsion added with the petroleum resin emulsifier provided by the invention is white in appearance, has an average particle size of 299-525 nm, and has no crusting and no water bleeding after being stored for 14 days at 55 ℃, while the C5 aqueous petroleum resin emulsion obtained by adopting the existing dodecylbenzene sulfonic acid and OP-10 as the emulsifier has a higher particle size and has the problem of crusting after being stored, which indicates that the storage stability is poor.
The aqueous petroleum resin emulsions obtained in application examples 11 to 20 and comparative application examples 3 to 4 were tested according to the above test method, and the test results are shown in table 2:
TABLE 2
| Appearance of the product | Average particle diameter/nm | Storage stability | |
| Application example 11 | White colour | 486 | No crusting and no bleeding |
| Application example 12 | White colour | 512 | No crusting and no bleeding |
| Application example 13 | White colour | 436 | No crusting and no bleeding |
| Application example 14 | White colour | 567 | No crusting and no precipitationWater (W) |
| Application example 15 | White colour | 515 | Without crusting and bleeding |
| Application example 16 | White colour | 533 | No crusting and no bleeding |
| Application example 17 | White colour | 426 | No crusting and no bleeding |
| Application example 18 | White colour | 502 | Without crusting and bleeding |
| Application example 19 | White colour | 585 | No crusting and no bleeding |
| Application example 20 | White colour | 674 | Without crusting and bleeding |
| Comparative application example 3 | White colour | 1467 | Skinning and bleeding |
| Comparative application example 4 | White colour | 1578 | Skinning and bleeding |
As can be seen from the data in tables 1 and 2:
the C9 aqueous petroleum resin emulsion added with the petroleum resin emulsifier provided by the invention is white in appearance, has an average particle size of 426-674 nm, and has no crusting and no water bleeding when stored for 14 days at 55 ℃, while the C9 aqueous petroleum resin emulsion obtained by adopting the existing dodecylbenzene sulfonic acid and OP-10 as the emulsifier has a higher particle size and has the problem of crusting after storage, which indicates that the storage stability is poor.
The applicant states that the present invention is illustrated by the above examples to a petroleum resin emulsifier and its preparation method and application, but the present invention is not limited to the above examples, i.e. it does not mean that the present invention must be implemented by the above examples. It should be understood by those skilled in the art that any modification of the present invention, equivalent substitutions of the raw materials of the product of the present invention, addition of auxiliary components, selection of specific modes, etc., are within the scope and disclosure of the present invention.
Claims (10)
1. The petroleum resin emulsifier is characterized in that raw materials for preparing the petroleum resin emulsifier comprise vegetable oil fatty acid, monohydric alcohol, an acid catalyst, a basic catalyst, an alcohol amine compound, cyclic anhydride and polymer polyol.
2. The petroleum resin emulsifier according to claim 1, wherein the vegetable oil fatty acid comprises any one or a combination of at least two of tung oil fatty acid, catalpa oil fatty acid, linseed oil fatty acid, perilla oil fatty acid, hemp oil fatty acid, soybean oil fatty acid, sunflower oil fatty acid, cottonseed oil fatty acid, corn oil fatty acid, coconut oil fatty acid, rice bran oil fatty acid, sesame oil fatty acid, castor oil fatty acid, peanut oil fatty acid, melon seed oil fatty acid, camellia seed oil fatty acid, peony seed oil fatty acid, palm oil fatty acid, walnut oil fatty acid, or olive oil fatty acid, preferably any one or a combination of at least two of palm oil fatty acid, coconut oil fatty acid, soybean oil fatty acid, hemp oil fatty acid, sunflower oil fatty acid, or walnut oil fatty acid;
preferably, the monohydric alcohol comprises any one of methanol, ethanol, n-propanol or isopropanol or a combination of at least two thereof, and is further preferably methanol and/or ethanol;
the molar ratio of the vegetable oil fatty acid to the monohydric alcohol is preferably 1 (2-8), more preferably 1 (4-6).
3. The petroleum resin emulsifier of claim 1 or 2, wherein the acidic catalyst comprises any one or a combination of at least two of sulfuric acid, p-toluenesulfonic acid, phosphoric acid, or propionic acid;
preferably, the basic catalyst comprises sodium hydroxide and/or potassium hydroxide.
4. Petroleum resin emulsifier according to any of the claims 1 to 3, wherein the alcamines compound comprises any one or a combination of at least two of isopropanolamine, ethanolamine, DL-aminopropanol, propanolamine, 1-amino-2-methyl-2-propanol, 3-aminon-butanol, 5-amino-1-pentanol, p-aminobenzyl alcohol, 2-aminobenzyl alcohol or 4-aminobenzyl alcohol, preferably p-aminobenzyl alcohol and/or 5-amino-1-pentanol;
preferably, the cyclic anhydride comprises any one or a combination of at least two of succinic anhydride, adipic anhydride, glutaric anhydride, tetrafluorosuccinic anhydride, butylsuccinic anhydride, 2-methylsuccinic anhydride, n-octylsuccinic anhydride, dodecylsuccinic anhydride, tetradecylsuccinic anhydride, hexadecylsuccinic anhydride, octadecylsuccinic anhydride or 2,2-dimethylsuccinic anhydride, and further preferably any one or a combination of at least two of succinic anhydride, glutaric anhydride or adipic anhydride;
preferably, the polymer polyol comprises polyethylene glycol;
preferably, the molar mass of the polyethylene glycol is 600 to 6000g/mol, more preferably 1000 to 2500g/mol.
5. A method for preparing the petroleum resin emulsifier according to any one of claims 1 to 4, wherein the method comprises the steps of:
(1) Reacting vegetable oil fatty acid with monohydric alcohol under the condition of an acid catalyst to obtain vegetable oil fatty acid ester;
(2) Reacting the vegetable oil fatty acid ester obtained in the step (1) with an alcohol amine compound under the condition of an alkaline catalyst to obtain vegetable oil fatty acid alcohol amide;
(3) Reacting the vegetable oil fatty acid alcohol amide obtained in the step (2) with cyclic acid anhydride to obtain an intermediate product;
(4) And (4) reacting the intermediate product obtained in the step (3) with polymer polyol under an acidic condition to obtain the petroleum resin emulsifier.
6. The method according to claim 5, wherein the temperature of the reaction in step (1) is 50 to 100 ℃;
preferably, the reaction in the step (1) is ended by the acid value of the system being not higher than 5 mgKOH/g;
preferably, the mass of the acid catalyst in the step (1) is 0.5 to 2% based on 100% of the mass of the vegetable oil fatty acid in the step (1).
7. The method according to claim 5 or 6, wherein the temperature of the reaction in the step (2) is 120 to 160 ℃;
preferably, the reaction time of the step (2) is 3-5 h;
preferably, the molar ratio of the vegetable oil fatty acid ester to the alcohol amine compound in the step (2) is 1 (1-1.5);
preferably, the mass of the basic catalyst in the step (2) is 0.5 to 2% based on 100% of the mass of the vegetable oil fatty acid ester in the step (2).
8. The method according to any one of claims 5 to 7, wherein the temperature of the reaction in the step (3) is 120 to 180 ℃;
preferably, the reaction time of the step (3) is 3-5 h;
preferably, the mass ratio of the vegetable oil fatty acid alcohol amide to the cyclic acid anhydride in the step (3) is 1 (0.5-1.5).
9. The process according to any one of claims 5 to 8, wherein the molar ratio of the polymer polyol to the intermediate product in the step (4) is (1-2: 1;
preferably, the temperature of the reaction in the step (4) is 150-220 ℃;
preferably, the reaction in the step (4) is ended by the acid value of the system being not higher than 5 mgKOH/g;
preferably, the mass of the acidic catalyst in the step (4) is 0.5 to 2% based on 100% of the mass of the intermediate in the step (4).
10. An aqueous petroleum resin emulsion comprising the petroleum resin emulsifier according to any one of claims 1 to 5, a petroleum resin and water;
preferably, the petroleum resin comprises a C5 petroleum resin and/or a C9 petroleum resin.
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