CN116102729B - A method for preparing star-shaped block structure polyether and polymer special surfactant - Google Patents
A method for preparing star-shaped block structure polyether and polymer special surfactant Download PDFInfo
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- CN116102729B CN116102729B CN202211624655.7A CN202211624655A CN116102729B CN 116102729 B CN116102729 B CN 116102729B CN 202211624655 A CN202211624655 A CN 202211624655A CN 116102729 B CN116102729 B CN 116102729B
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- 229920000642 polymer Polymers 0.000 title claims abstract description 65
- 229920000570 polyether Polymers 0.000 title claims abstract description 49
- 239000004721 Polyphenylene oxide Substances 0.000 title claims abstract description 48
- 239000004094 surface-active agent Substances 0.000 title claims abstract description 47
- 238000000034 method Methods 0.000 title claims description 19
- ULQISTXYYBZJSJ-UHFFFAOYSA-N 12-hydroxyoctadecanoic acid Chemical compound CCCCCCC(O)CCCCCCCCCCC(O)=O ULQISTXYYBZJSJ-UHFFFAOYSA-N 0.000 claims abstract description 60
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical compound C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 claims abstract description 47
- GOOHAUXETOMSMM-UHFFFAOYSA-N Propylene oxide Chemical compound CC1CO1 GOOHAUXETOMSMM-UHFFFAOYSA-N 0.000 claims abstract description 37
- 229940114072 12-hydroxystearic acid Drugs 0.000 claims abstract description 30
- 239000003999 initiator Substances 0.000 claims abstract description 24
- 238000002360 preparation method Methods 0.000 claims abstract description 15
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims abstract description 14
- 238000007151 ring opening polymerisation reaction Methods 0.000 claims abstract description 7
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 73
- 238000006243 chemical reaction Methods 0.000 claims description 42
- 229910052757 nitrogen Inorganic materials 0.000 claims description 35
- 238000003756 stirring Methods 0.000 claims description 27
- KWYUFKZDYYNOTN-UHFFFAOYSA-M potassium hydroxide Substances [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 25
- 239000002253 acid Substances 0.000 claims description 22
- 239000003054 catalyst Substances 0.000 claims description 22
- 238000010438 heat treatment Methods 0.000 claims description 16
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 claims description 15
- 238000001816 cooling Methods 0.000 claims description 12
- 238000007599 discharging Methods 0.000 claims description 12
- 239000000047 product Substances 0.000 claims description 12
- JOXIMZWYDAKGHI-UHFFFAOYSA-N p-toluenesulfonic acid Substances CC1=CC=C(S(O)(=O)=O)C=C1 JOXIMZWYDAKGHI-UHFFFAOYSA-N 0.000 claims description 10
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 claims description 9
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 9
- PEDCQBHIVMGVHV-UHFFFAOYSA-N glycerol group Chemical group OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 claims description 9
- 238000006116 polymerization reaction Methods 0.000 claims description 9
- 239000002904 solvent Substances 0.000 claims description 9
- 239000000376 reactant Substances 0.000 claims description 6
- JNYAEWCLZODPBN-JGWLITMVSA-N (2r,3r,4s)-2-[(1r)-1,2-dihydroxyethyl]oxolane-3,4-diol Chemical compound OC[C@@H](O)[C@H]1OC[C@H](O)[C@H]1O JNYAEWCLZODPBN-JGWLITMVSA-N 0.000 claims description 5
- -1 alkyl glycoside Chemical class 0.000 claims description 5
- 239000007788 liquid Substances 0.000 claims description 5
- 238000002844 melting Methods 0.000 claims description 5
- 230000008018 melting Effects 0.000 claims description 5
- 230000007935 neutral effect Effects 0.000 claims description 5
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims description 4
- SQUHHTBVTRBESD-UHFFFAOYSA-N Hexa-Ac-myo-Inositol Natural products CC(=O)OC1C(OC(C)=O)C(OC(C)=O)C(OC(C)=O)C(OC(C)=O)C1OC(C)=O SQUHHTBVTRBESD-UHFFFAOYSA-N 0.000 claims description 3
- 239000007795 chemical reaction product Substances 0.000 claims description 3
- 229930182470 glycoside Natural products 0.000 claims description 3
- CDAISMWEOUEBRE-GPIVLXJGSA-N inositol Chemical compound O[C@H]1[C@H](O)[C@@H](O)[C@H](O)[C@H](O)[C@@H]1O CDAISMWEOUEBRE-GPIVLXJGSA-N 0.000 claims description 3
- 229960000367 inositol Drugs 0.000 claims description 3
- WXZMFSXDPGVJKK-UHFFFAOYSA-N pentaerythritol Chemical compound OCC(CO)(CO)CO WXZMFSXDPGVJKK-UHFFFAOYSA-N 0.000 claims description 3
- CDAISMWEOUEBRE-UHFFFAOYSA-N scyllo-inosotol Natural products OC1C(O)C(O)C(O)C(O)C1O CDAISMWEOUEBRE-UHFFFAOYSA-N 0.000 claims description 3
- 239000000126 substance Substances 0.000 claims description 3
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims description 2
- 238000007600 charging Methods 0.000 claims description 2
- 238000005259 measurement Methods 0.000 claims description 2
- 238000002156 mixing Methods 0.000 claims description 2
- 125000005489 p-toluenesulfonic acid group Chemical group 0.000 claims description 2
- 239000012265 solid product Substances 0.000 claims description 2
- 239000002480 mineral oil Substances 0.000 abstract description 22
- 235000010446 mineral oil Nutrition 0.000 abstract description 22
- 239000000839 emulsion Substances 0.000 abstract description 19
- 239000013530 defoamer Substances 0.000 abstract description 10
- 230000002045 lasting effect Effects 0.000 abstract description 3
- 230000002194 synthesizing effect Effects 0.000 abstract 1
- 239000000243 solution Substances 0.000 description 13
- 238000012360 testing method Methods 0.000 description 9
- 230000000694 effects Effects 0.000 description 7
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 6
- 238000012512 characterization method Methods 0.000 description 5
- 238000005886 esterification reaction Methods 0.000 description 5
- 230000015572 biosynthetic process Effects 0.000 description 4
- 239000003921 oil Substances 0.000 description 4
- KJFMBFZCATUALV-UHFFFAOYSA-N phenolphthalein Chemical compound C1=CC(O)=CC=C1C1(C=2C=CC(O)=CC=2)C2=CC=CC=C2C(=O)O1 KJFMBFZCATUALV-UHFFFAOYSA-N 0.000 description 4
- 238000003786 synthesis reaction Methods 0.000 description 4
- 238000004448 titration Methods 0.000 description 4
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 229910001873 dinitrogen Inorganic materials 0.000 description 3
- 230000032050 esterification Effects 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 238000010992 reflux Methods 0.000 description 3
- 238000005070 sampling Methods 0.000 description 3
- 239000007787 solid Substances 0.000 description 3
- 239000012086 standard solution Substances 0.000 description 3
- 229920001131 Pulp (paper) Polymers 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 238000004364 calculation method Methods 0.000 description 2
- 238000013461 design Methods 0.000 description 2
- 235000014113 dietary fatty acids Nutrition 0.000 description 2
- 239000000194 fatty acid Substances 0.000 description 2
- 229930195729 fatty acid Natural products 0.000 description 2
- 230000002349 favourable effect Effects 0.000 description 2
- 238000005187 foaming Methods 0.000 description 2
- 239000012046 mixed solvent Substances 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 238000004537 pulping Methods 0.000 description 2
- WGIMXKDCVCTHGW-UHFFFAOYSA-N 2-(2-hydroxyethoxy)ethyl dodecanoate Chemical compound CCCCCCCCCCCC(=O)OCCOCCO WGIMXKDCVCTHGW-UHFFFAOYSA-N 0.000 description 1
- 229920003171 Poly (ethylene oxide) Polymers 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 238000007334 copolymerization reaction Methods 0.000 description 1
- 230000001804 emulsifying effect Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 150000004665 fatty acids Chemical class 0.000 description 1
- 235000013373 food additive Nutrition 0.000 description 1
- 239000002778 food additive Substances 0.000 description 1
- 230000002209 hydrophobic effect Effects 0.000 description 1
- 239000010423 industrial mineral Substances 0.000 description 1
- 229920002521 macromolecule Polymers 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 238000000691 measurement method Methods 0.000 description 1
- 229920000223 polyglycerol Polymers 0.000 description 1
- FZJCXIDLUFPGPP-UHFFFAOYSA-N propan-2-ol;toluene Chemical compound CC(C)O.CC1=CC=CC=C1 FZJCXIDLUFPGPP-UHFFFAOYSA-N 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 235000012239 silicon dioxide Nutrition 0.000 description 1
- 238000013112 stability test Methods 0.000 description 1
- 239000003381 stabilizer Substances 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
- 238000005303 weighing Methods 0.000 description 1
Classifications
-
- D—TEXTILES; PAPER
- D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
- D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
- D21H21/00—Non-fibrous material added to the pulp, characterised by its function, form or properties; Paper-impregnating or coating material, characterised by its function, form or properties
- D21H21/14—Non-fibrous material added to the pulp, characterised by its function, form or properties; Paper-impregnating or coating material, characterised by its function, form or properties characterised by function or properties in or on the paper
- D21H21/22—Agents rendering paper porous, absorbent or bulky
- D21H21/24—Surfactants
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G65/00—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule
- C08G65/02—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring
- C08G65/26—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring from cyclic ethers and other compounds
- C08G65/2603—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring from cyclic ethers and other compounds the other compounds containing oxygen
- C08G65/2606—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring from cyclic ethers and other compounds the other compounds containing oxygen containing hydroxyl groups
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G81/00—Macromolecular compounds obtained by interreacting polymers in the absence of monomers, e.g. block polymers
Landscapes
- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Polyethers (AREA)
- Cosmetics (AREA)
- Emulsifying, Dispersing, Foam-Producing Or Wetting Agents (AREA)
Abstract
The invention discloses a preparation method of star-shaped block structure polyether and a polymer special surfactant, which comprises the steps of selecting polyhydroxy (hydroxyl number is more than or equal to 3) initiator with a star-shaped structure, preparing penta-block polyether by ring-opening polymerization with Ethylene Oxide (EO) and Propylene Oxide (PO), and synthesizing the block polyether and a specific molecular weight 12-hydroxystearic acid self-polymer into the polymer special surfactant with the star-shaped structure. The mineral oil defoamer emulsion formula of the polymer special surfactant has lasting stability and appearance uniformity.
Description
Technical Field
The invention belongs to the technical field of paper pulp and paper making, and particularly relates to a special polymer surfactant modification technology in a mineral oil defoamer in paper pulp and paper making.
Background
The current mineral oil defoamer is widely applied in the pulping and papermaking field, but the mineral oil defoamer has the phenomena of poor appearance uniformity or non-durable stability of emulsion in the use process, so that the defoaming effect is limited in the subsequent use process, and better effect is difficult to exert.
The addition of surfactants to mineral oils to improve the uniform stability of mineral oil defoamer emulsions has become a consensus in the pulping and papermaking arts. However, the existing surfactants on the market still have the problems of general use effect, difficulty in maintaining the lasting stability of the mineral oil emulsion or higher price of the surfactants, so that the special surfactants which can be effectively used for industrial mineral oil in actual production and keep the emulsion with better stability are less.
Disclosure of Invention
Aiming at the problems existing in the prior art, the invention aims to provide a preparation method of star-type block structure polyether and a polymer special surfactant.
In order to solve the technical problems, the invention adopts the following technical scheme: a star block structured polyether having the chemical structural formula:
r- (O-EO m-POX-EOn-POy-EOq-H)i or
Wherein R is a main chain structure of a polyhydroxy initiator with a hydroxyl number more than or equal to 3, i is the hydroxyl number of the polyhydroxy initiator, E0 is ethylene oxide, P0 is propylene oxide, and the polymerization degree m=n=q is within a value range of 1-4; the polymerization degree x=y, and the value range is 1-4; and (m+n+q) > (x+y);
wherein a=b=c=1 to 3,w =z=2 to 5, the values are integers, and (a+b+c) < (w+z).
Preferably, the polyhydroxy initiator is glycerol, pentaerythritol, sorbitan, alkyl glycoside, inositol or triglycerin.
Preferably, the molecular weight of the polyether with the block structure ranges from 1200 to 3200.
As a preferable scheme, the molar ratio of the polyhydroxy initiator to E0 is 1:9-1:40, and the molar ratio of EO to PO is more than or equal to 3:2.
The invention also provides a preparation method of the special polymer surfactant based on the polyether with the block structure, which comprises the following steps:
Step S1, preparing star block polyether: adding a proper amount of polyhydroxy initiator, solvent and catalyst into a reactor, stirring uniformly at 20-100 ℃, introducing nitrogen to maintain an anaerobic environment, heating the system to 100-140 ℃, adding EO and PO into the system for ring-opening polymerization reaction for 5 times under the protection of nitrogen, continuing to react for 10-90 min after EO and PO are added, stopping introducing nitrogen, cooling the system to below 100 ℃, adding a proper amount of citric acid to adjust the pH of the system to be neutral, and discharging to obtain star-type block polyether product;
step S2, preparation of 12-hydroxystearic acid self-polymer: adding 12-hydroxystearic acid and a catalyst into a reactor, stirring and melting at 75-120 ℃ to form a uniform solution, heating the system to 120-150 ℃ under the protection of nitrogen, performing self-polymerization for 6-15 h, controlling the molecular weight range of the self-polymer according to the acid value of the measured system, and stopping introducing nitrogen when the molecular weight of the self-polymer reaches 2000-6000 to obtain a brown yellow opaque liquid of the 12-hydroxystearic acid self-polymer;
Step S3, preparing a polymer special surfactant: and (3) adding the 12-hydroxystearic acid self-polymer obtained in the step (S2) and a catalyst into a reactor, stirring and mixing to form a uniform solution, heating to 120-150 ℃ under the protection of nitrogen, adding the obtained product into the step (S1) to obtain a star-block polyether product, reacting for 6-15h under stirring, controlling the molecular weight of the reaction product to be 7000-39000 according to the acid value of a measurement system, stopping nitrogen charging and discharging, and cooling to obtain the star-polymer special surfactant solid product.
Preferably, the same catalyst is adopted in the steps S2 and S3, the catalyst is p-toluenesulfonic acid or phosphoric acid, and the addition amount of the catalyst is 0.1-2% of the total weight of reactants.
Preferably, the catalyst in the step S1 is KOH or NaOH, and the addition amount of the catalyst is 0.1-3% of the total weight of reactants; the solvent adopts dimethyl sulfoxide, and the mass ratio of the polyhydroxy initiator to the solvent is 1:2-1:3.
Preferably, the mole ratio of the star block polyether product to the 12-hydroxystearic acid self-polymer in the step S3 is 1:3-1:20.
Preferably, in step S1, the EO is added to the reaction system in three portions, the PO is added to the reaction system in two portions, and the EO and PO are added at alternating intervals.
Preferably, in step S1, the EO is added to the reaction system in two portions, the PO is added to the reaction system in three portions, and the EO and PO are added at alternating intervals.
The beneficial effects are that: compared with the prior art, the invention has the following advantages:
1. Polyhydroxy (hydroxyl number is more than or equal to 3) initiator with branched chain (star) structure is selected, and Ethylene Oxide (EO) and Propylene Oxide (PO) are grafted under certain process conditions to carry out ring-opening polymerization reaction, so that polyether with (star) block structure is prepared. Compared with A hydroxyl-containing initiator with A linear structure, A polyhydroxy (hydroxyl number is more than or equal to 3) initiator with A branched structure has more grafting sites, can be connected with A plurality of EO and PO groups according to the requirement, and forms A five-segment EO/PO chain segment with A-B-A-B-A, meanwhile, compared with A traditional three-segment EO/PO chain segment with A-B-A, the block polyether structure has better stability, and is also beneficial to the subsequent graft copolymerization with acid self-polymers.
2. The EO hydrophilicity is good, the foaming effect is good, and the PO hydrophilicity is relatively poor, so in the polyether block design of the invention, the inventor innovates that the EO amount is larger than the PO amount, and plays a key role in the subsequent synthesis of the polymer special surfactant with a star structure and the better appearance uniformity and stability of emulsion in the use of the mineral oil defoamer. In addition, the inventors have found that block polyethers have a better effect, especially in the molecular weight range 1200 to 3200.
3. The self-polymer of 12-hydroxystearic acid with specific molecular weight range (2000-6000) is prepared by controlling the technological conditions, compared with the self-polymer of 12-hydroxystearic acid with low molecular weight which is directly used for reacting with the polyether, the self-polymerized 12-hydroxystearic acid (i.e. self-polymer) has more stable structure, and the formed macromolecular substance with specific molecular weight range is more favorable for obtaining star-shaped polymer special surfactant with lower acid value in the subsequent esterification reaction, and meanwhile, the self-polymer is favorable for the subsequent synthesis of the polymer special surfactant with specific molecular weight range.
4. The star-type block structure polyether with specific molecular weight range and designed structure and the 12-hydroxystearic acid self-polymer are subjected to esterification reaction under certain technological conditions to synthesize the special polymer surfactant with specific molecular weight range (7000-39000 and acid value of 1-10 mgKOH/g). The special polymer surfactant with the specific molecular weight can ensure that the mineral oil defoamer emulsion has better appearance uniformity and high-temperature stability when in use, can be stably placed for more than 6 months at 55 ℃, and solves the problem that the stability of the current mineral oil defoamer emulsion is limited.
Detailed Description
The application will be further elucidated with reference to specific examples. It is to be understood that these examples are for the purpose of illustrating the application only and are not to be construed as limiting the scope of the application, since modifications to the application, which are various equivalent to those skilled in the art, will fall within the scope of the application as defined in the appended claims after reading the application.
Substance chinese-english name contrast:
polyoxyethylene fatty acid LAE
Diethylene glycol monolaurate PEG-2
The invention relates to a polymer special surfactant which is applied to a mineral oil type defoamer for papermaking, and the synthesis process of the polymer special surfactant mainly comprises the following steps:
1. preparation of Star block polyether (C):
Adding a proper amount of polyhydroxy (hydroxyl number is more than or equal to 3) initiator with a branched chain (star-shaped) structure, solvent and catalyst into a reactor with a thermometer, a stirring paddle and a reflux condensing device, stirring uniformly at 20-100 ℃, continuously introducing nitrogen into the system after the system is vacuumized and nitrogen is introduced for several times, keeping an anaerobic environment, and slowly heating the system to 100-140 ℃.
EO and PO should be added in portions under nitrogen to effect the reaction. Adding 1/3 of EO for the first time, slowly adding 1/5 EO, stirring for reacting for 5-15 min, slowly introducing the residual 4/5 EO for the first time, and continuously carrying out ring-opening polymerization for 10-45min; slowly adding 1/2 of PO, and continuing the reaction for 10-45min; slowly adding 1/3 EO for the second time, and continuing the reaction for 10-45min; slowly adding the rest 1/2 of PO, and continuing the reaction for 10-45min; slowly adding the residual 1/3 EO for the third time, and continuing the reaction for 10-90 min; and then stopping nitrogen gas introduction, cooling the system to below 100 ℃, adding a proper amount of citric acid to adjust the pH of the system to neutral, and discharging to obtain star-block polyether C (the single chain segment structure is an initiator RO-EOm-POx-EOn-POy-EOq-H).
In the process, the polyhydroxy (hydroxyl number is more than or equal to 3) initiator with the branched chain structure can adopt any one of glycerol, pentaerythritol, sorbitan, alkyl glycoside, inositol, triglycerin and the like; the solvent adopted in the reaction system is dimethyl sulfoxide, the catalyst is KOH or NaOH, and the most preferable addition amount is 0.1-1.5%. What is important is: the molar ratio of the initiator to the total EO is preferably 1:9-1:40, and the molar ratio of the total EO to the total PO is not less than 3:2, namely: EO accounts for at least more than 60%, and because EO is good in hydrophilicity, foaming effect is good, PO is relatively poor in hydrophilicity, EO amount is larger than PO amount in polyether block design, and the EO is also key to subsequent synthesis of star-structured polymer special surfactants and better appearance uniformity and stability of emulsion in use of mineral oil defoamer.
Similarly, the sequence of changing the adding sequence to PO, EO, PO, EO and then PO according to the above-mentioned steps and a certain proportion is also suitable for preparing the structural star-block polyether C (the single hydroxyl-containing chain segment structure is RO-POa-EOw-POb-EOz-POc-H).
2. Preparation of 12-hydroxystearic acid self-polymer (H) having a specific molecular weight range:
adding a proper amount of 12-hydroxystearic acid and a catalyst into a four-neck flask with a thermometer and a stirring paddle, melting in an oil bath at 75-120 ℃, starting stirring until the solution is uniform, introducing nitrogen into the system, after the system is air-emptied stably (acid value before sampling and measuring reaction), heating the system to 120-150 ℃, reacting for self-polymerization for 6-15H at a specified temperature, measuring the acid value of the system at intervals (obtaining a self-polymer meeting the molecular weight range requirement) in the process, stopping the reaction until meeting the requirement, stopping introducing nitrogen, cooling and discharging to obtain a brown yellow impermeable liquid, namely the 12-hydroxystearic acid self-polymer H.
3. Preparation of Star-shaped Polymer Special surfactant (S)
The 12 hydroxystearic acid self-polymer (i.e., H) obtained by the reaction of 2 and the catalyst were put into a four-port reactor equipped with a stirring paddle and a thermometer, and stirred at 85℃and 200rpm until the solution was uniform. Introducing nitrogen into the system, and heating to 120-150 ℃ after the air of the system is emptied stably; adding a proper amount of block polyether (namely C) into a reactor, and stirring to a uniform state; the materials react for 6 to 15 hours at constant temperature, the acid value of the system is tested at regular intervals in the process until the reaction is stopped according with the requirements, the nitrogen is stopped from being introduced, the temperature is reduced, and the sample is a blocky solid at room temperature, namely the star polymer special surfactant S.
Example 1:
1. Preparation of Star-block polyether:
adding 1mol of sorbitan, 330g of dimethyl sulfoxide and 0.6% of KOH catalyst into a reactor with a thermometer, a stirring paddle and a reflux condensing device, stirring uniformly at 90 ℃, continuously introducing nitrogen into the system after the system is vacuumized and nitrogen is introduced for several times repeatedly, keeping an anaerobic environment, and slowly heating the system to 110 ℃;
the reaction should be carried out by adding 26mol and 17mol of EO and PO in each case in batches under nitrogen protection. Adding 1/3 of total EO for the first time, slowly adding 1/5 of EO, stirring for reacting for 10min, slowly introducing the residual 4/5 of EO for the first time, and continuously performing ring-opening polymerization on the system for 30min; slowly adding 1/2 of PO, and continuing the reaction for 30min; slowly adding 1/3 EO for the second time, and continuing the reaction for 30min; slowly adding the rest 1/2 of PO, and continuing the reaction for 30min; slowly adding the rest 1/3 EO for the third time, and continuing the reaction for 60min; and stopping nitrogen gas introduction, cooling the system to below 100 ℃, adding a proper amount of citric acid to adjust the pH of the system to neutral, and discharging to obtain the star-block polyether C1 (wherein EO/PO structures in a single hydroxyl chain segment are represented by an initiator EO 2-PO2-EO2-PO2-EO2). And (3) detecting: the molecular weight of the star block polyether C1 obtained in this example was 2193.
2. Preparation of 12-hydroxystearic acid self-polymers having a specific molecular weight range:
Adding 300g of 12-hydroxystearic acid and 0.5% of p-toluenesulfonic acid into a four-neck flask with a thermometer and a stirring paddle, melting in an oil bath at 90 ℃, starting stirring until the solution is uniform, introducing nitrogen into the system, after the system is air-emptied stably (acid value before sampling and measuring reaction), heating the system to 145 ℃, reacting for self-polymerization for 8 hours at a specified temperature, testing the acid value of the system at regular intervals in the process until the reaction is terminated according to the requirement, stopping introducing nitrogen, cooling and discharging to obtain a brown yellow impermeable liquid, namely 12-hydroxystearic acid self-polymer H1, and measuring the molecular weight to be 3614.
3. Preparation of star polymer special surfactant
10Mol of 12 hydroxystearic acid self-polymer H1 and 0.5% of p-toluenesulfonic acid were charged into a four port reactor equipped with a stirrer and a thermometer and stirred at 85℃and 200rpm until the solution became homogeneous. Introducing nitrogen into the system, and heating to 145 ℃ after the air of the system is emptied stably; 1mol of the block polyether was charged into a reactor and stirred to a uniform state; and (3) carrying out constant-temperature reaction on the materials for 12 hours, testing the acid value of the system at regular intervals in the process until the reaction is stopped according with the requirements, stopping introducing nitrogen, cooling and discharging, wherein the sample is a massive solid at room temperature, namely the star-shaped polymer special surfactant S1.
Example 2:
1. Preparation of Star-block polyether:
adding 1mol of sorbitan, 330g of dimethyl sulfoxide and 0.6% of KOH catalyst into a reactor with a thermometer, a stirring paddle and a reflux condensing device, stirring uniformly at 90 ℃, continuously introducing nitrogen into the system after the system is vacuumized and nitrogen is introduced for several times repeatedly, keeping an anaerobic environment, and slowly heating the system to 110 ℃;
the reaction should be carried out by adding 25mol of EO and 13mol of PO in portions under nitrogen. Adding 1/3 of the total amount of PO for the first time, slowly adding 1/5 of the PO, stirring and reacting for 10min, slowly introducing the remaining 4/5 of the PO for the first time, and continuously performing ring-opening polymerization on the system for 30min; slowly adding 1/2 EO, and continuing the reaction for 30min; slowly adding 1/3 of PO for the second time, and continuing the reaction for 30min; slowly adding the rest 1/2 EO, and continuing the reaction for 30min; slowly adding the rest 1/3 of PO for the third time, and continuing the reaction for 60min; and stopping nitrogen gas introduction, cooling the system to below 100 ℃, adding a proper amount of citric acid to adjust the pH of the system to neutral, and discharging to obtain the star-block polyether C2 (wherein EO/PO structures in a single hydroxyl chain segment: an initiator-PO 1-EO3-PO1-EO3-PO1). And (3) detecting: the molecular weight of star block polyether C2 obtained in this example was 1930.
2. Preparation of 12-hydroxystearic acid self-polymers having a specific molecular weight range:
Adding 300g of 12-hydroxystearic acid and 0.5% of p-toluenesulfonic acid into a four-neck flask with a thermometer and a stirring paddle, melting in an oil bath at 90 ℃, starting stirring until the solution is uniform, introducing nitrogen into the system, after the system is air-emptied stably (acid value before sampling and measuring reaction), heating the system to 145 ℃, reacting for self-polymerization for 8 hours at a specified temperature, testing the acid value of the system at regular intervals in the process until the reaction is terminated according to the requirement, stopping introducing nitrogen, cooling and discharging to obtain a brown yellow impermeable liquid, namely 12-hydroxystearic acid self-polymer H2, and measuring the molecular weight to be 3614.
3. Preparation of star polymer special surfactant
10Mol of 12 hydroxystearic acid self-polymer H1 and 0.5% of p-toluenesulfonic acid were charged into a four port reactor equipped with a stirrer and a thermometer and stirred at 85℃and 200rpm until the solution became homogeneous. Introducing nitrogen into the system, and heating to 145 ℃ after the air of the system is emptied stably; 1mol of the block polyether was charged into a reactor and stirred to a uniform state; and (3) carrying out constant-temperature reaction on the materials for 12 hours, testing the acid value of the system at regular intervals in the process until the reaction is stopped according with the requirements, stopping introducing nitrogen, cooling and discharging, wherein the sample is a massive solid at room temperature, namely the star polymer special surfactant S2.
Examples 3 to 15:
In examples 3-15, the (star) polymer specialty surfactant was prepared by a procedure different from example 1 in that: the initiator, the ratio of addition of ethylene oxide EO and propylene oxide PO, the order of addition, the molecular weight of the block polyether, or the molecular weight of the 12-hydroxystearic acid self-polymer are different, and the rest are the same. In each example, the reactants and the amounts added are shown in Table 1, and the basic product indices of the resulting surfactant products are shown in tables 2 and 3.
Table 1: reactant addition amounts and reaction times in the examples
Table 2: the block polyether structures and molecular weights obtained in the examples
Table 3 shows the product index of the special surfactant obtained in each example
The special surfactant S prepared in examples 1-15 was prepared as follows to give mineral oil emulsions: adding proper amounts of 15# white oil, hydrophobic silicon dioxide, D10, a special surfactant S and water into a four-neck flask with a thermometer and a stirring paddle in sequence, reacting, emulsifying and stirring uniformly at 80-150 ℃ for 10-90 min to obtain mineral oil emulsion M, and evaluating the stability of the mineral oil emulsion. Wherein the formula of each component in the mineral oil emulsion is as follows:
then, the mineral oil emulsion properties were tested as shown in table 4:
table 4: properties and product index of mineral oil emulsions prepared in the examples
Characterization of the properties:
the performance characterization test is carried out on the surfactant with characteristic reaction products obtained in each example, and the characterization test method is as follows:
(1) Characterization of synthetic specialty surfactant properties
Appearance: the appearance of the sample was visually observed and recorded at room temperature.
The acid value testing method comprises the following steps: preparing a mixed solvent consisting of equal volume of isopropanol and toluene, a 1% phenolphthalein isopropanol solution and a 0.1mol/L potassium hydroxide standard titration solution by referring to annex A of food additive polyglycerol fatty acid ester; 50mL of isopropanol-toluene solvent was placed in a conical flask, and 2mL of 1% phenolphthalein isopropanol solution was added; titration with 0.1mol/L potassium hydroxide standard solution until the solution becomes pink, accurately weighing 0.3-0.5g of sample, marking as W, dissolving in mixed solvent, heating if necessary, shaking vigorously, titration with 0.1mol/L potassium hydroxide standard solution, taking the pink solution as the end point, recording the volume of the consumed potassium hydroxide standard solution when the titration is carried out, and marking as V. The calculation formula of the acid value X1 is as follows:
The esterification rate testing method comprises the following steps: according to the acid value change of the system before and after the reaction, the esterification rate is calculated according to the following calculation formula:
Esterification rate= (acid value of system before reaction-acid value of system after reaction end)/acid value of system before reaction x 100% molecular weight measurement method: samples were characterized for molecular weight testing using agilent type 1260 GPC.
(2) Characterization of the application Properties of surfactants in mineral oil emulsions
Stability test: and (3) taking a proper amount of the prepared mineral oil emulsion, and testing the stability performance of the mineral oil emulsion at the high temperature of 55 ℃ by using a Landson Turkiscan TOWER type stabilizer.
From the above examples and comparative examples, it can be seen that: the initiator with a branched chain structure (the hydroxyl number is more than or equal to 3), the five-segment block polyether C with a star-shaped structure and a 12-hydroxystearic acid self-polymer H with a specific molecular weight, which are synthesized by EO and PO, can help to generate a special surfactant S with a certain molecular weight; the above-mentioned desirable specialty surfactants S have a more uniform appearance and longer lasting high temperature stability in mineral oil emulsions than other linear structure initiators, 12-hydroxystearic acid self-polymers having molecular weights outside the range, single surfactants, and the like.
Claims (9)
1. A star block structured polyether characterized by the following chemical structural formula:
Or (b)
，
Wherein R is a main chain structure of a polyhydroxy initiator with a hydroxyl number more than or equal to 3, i is the hydroxyl number of the polyhydroxy initiator, EO is ethylene oxide, PO is propylene oxide, and the polymerization degree m=n=q is within a value range of 1-4; the polymerization degree x=y, and the value range is 1-4; and (m+n+q) > (x+y);
Wherein a=b=c=1 to 3, w=z=2 to 5, the value is an integer, and (a+b+c) < (w+z); the molecular weight of the block structure polyether ranges from 1200 to 3200.
2. The star block polyether of claim 1, wherein: the polyhydroxy initiator is glycerol, pentaerythritol, sorbitan, alkyl glycoside, inositol or triglycerin.
3. The star block polyether of claim 1, wherein: the molar ratio of the polyhydroxy initiator to EO is 1:9-1:40, and the molar ratio of EO to PO is equal to or greater than 3:2.
4. A method for preparing a special polymer surfactant based on the polyether with a block structure according to any one of claims 1-3, which is characterized by comprising the following steps:
Step S1, preparing star block polyether: adding a proper amount of polyhydroxy initiator, solvent and catalyst into a reactor, stirring uniformly at 20-100 ℃, introducing nitrogen to maintain an anaerobic environment, heating the system to 100-140 ℃, adding EO and PO into the system for ring-opening polymerization reaction for 5 times under the protection of nitrogen, continuing to react for 10-90 min after EO and PO are added, stopping introducing nitrogen, cooling the system to below 100 ℃, adding a proper amount of citric acid to adjust the pH of the system to be neutral, and discharging to obtain a star-type block polyether product;
Step S2, preparation of 12-hydroxystearic acid self-polymer: adding 12-hydroxystearic acid and a catalyst into a reactor, stirring and melting at 75-120 ℃ to form a uniform solution, heating the system to 120-150 ℃ under the protection of nitrogen, performing self-polymerization for 6-15 h, controlling the molecular weight range of the self-polymer according to the acid value of the measured system, and stopping introducing nitrogen when the molecular weight of the self-polymer reaches 2000-6000, so as to obtain a brown opaque liquid of the 12-hydroxystearic acid self-polymer;
Step S3, preparing a polymer special surfactant: and (3) adding the 12-hydroxystearic acid self-polymer obtained in the step (S2) and a catalyst into a reactor, stirring and mixing to form a uniform solution, heating to 120-150 ℃ under the protection of nitrogen, adding the obtained product into the step (S1) to obtain a star-block polyether product, reacting for 6-15h under stirring, controlling the molecular weight of the reaction product to be 7000-39000 according to the acid value of a measurement system, stopping nitrogen charging and discharging, and cooling to obtain the star-polymer special surfactant solid product.
5. The method for preparing the special polymer surfactant of the polyether with the block structure according to claim 4, which is characterized in that: the same catalyst is adopted in the steps S2 and S3, the catalyst is p-toluenesulfonic acid or phosphoric acid, and the addition amount of the catalyst is 0.1-2% of the total weight of reactants.
6. The method for preparing the special polymer surfactant of the polyether with the block structure according to claim 4, which is characterized in that: the catalyst in the step S1 adopts KOH or NaOH, and the addition amount of the catalyst is 0.1-3% of the total weight of reactants; the solvent adopts dimethyl sulfoxide, and the mass ratio of the polyhydroxy initiator to the solvent is 1:2-1:3.
7. The method for preparing the special polymer surfactant of the polyether with the block structure according to claim 4, which is characterized in that: the mole ratio of the star block polyether product to the 12-hydroxystearic acid self-polymer in the step S3 is 1:3-1:20.
8. The method for preparing the special polymer surfactant of the polyether with the block structure according to claim 4, which is characterized in that: in step S1, EO is added to the reaction system in three portions, PO is added to the reaction system in two portions, and EO and PO are added at alternating intervals.
9. The method for preparing the special polymer surfactant of the polyether with the block structure according to claim 4, which is characterized in that: in step S1, EO is added to the reaction system in two portions, PO is added to the reaction system in three portions, and EO and PO are added at alternating intervals.
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