CN109627434B - Preparation method of inorganic modified polyether polyol - Google Patents
Preparation method of inorganic modified polyether polyol Download PDFInfo
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- CN109627434B CN109627434B CN201811540413.3A CN201811540413A CN109627434B CN 109627434 B CN109627434 B CN 109627434B CN 201811540413 A CN201811540413 A CN 201811540413A CN 109627434 B CN109627434 B CN 109627434B
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- 229920005862 polyol Polymers 0.000 title claims abstract description 126
- 150000003077 polyols Chemical class 0.000 title claims abstract description 126
- 239000004721 Polyphenylene oxide Substances 0.000 title claims abstract description 124
- 229920000570 polyether Polymers 0.000 title claims abstract description 124
- 238000002360 preparation method Methods 0.000 title claims abstract description 13
- 239000002270 dispersing agent Substances 0.000 claims abstract description 33
- 239000000463 material Substances 0.000 claims abstract description 31
- 239000000843 powder Substances 0.000 claims abstract description 22
- 150000003242 quaternary ammonium salts Chemical class 0.000 claims abstract description 22
- 150000003512 tertiary amines Chemical class 0.000 claims abstract description 18
- 239000003054 catalyst Substances 0.000 claims abstract description 17
- 150000001335 aliphatic alkanes Chemical class 0.000 claims abstract description 16
- 150000007524 organic acids Chemical class 0.000 claims abstract description 14
- 230000009471 action Effects 0.000 claims abstract description 6
- 125000001302 tertiary amino group Chemical group 0.000 claims abstract 7
- 238000006243 chemical reaction Methods 0.000 claims description 91
- 238000000034 method Methods 0.000 claims description 29
- 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 25
- 238000003756 stirring Methods 0.000 claims description 21
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 19
- 230000008569 process Effects 0.000 claims description 13
- INQOMBQAUSQDDS-UHFFFAOYSA-N iodomethane Chemical group IC INQOMBQAUSQDDS-UHFFFAOYSA-N 0.000 claims description 8
- 230000035484 reaction time Effects 0.000 claims description 7
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims description 6
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 6
- RDHPKYGYEGBMSE-UHFFFAOYSA-N bromoethane Chemical compound CCBr RDHPKYGYEGBMSE-UHFFFAOYSA-N 0.000 claims description 5
- 229920006395 saturated elastomer Polymers 0.000 claims description 5
- 239000000377 silicon dioxide Substances 0.000 claims description 5
- 150000001875 compounds Chemical class 0.000 claims description 4
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 claims description 4
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 4
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 4
- 239000002245 particle Substances 0.000 claims description 4
- 235000012239 silicon dioxide Nutrition 0.000 claims description 4
- GRWPYGBKJYICOO-UHFFFAOYSA-N 2-methylpropan-2-olate;titanium(4+) Chemical compound [Ti+4].CC(C)(C)[O-].CC(C)(C)[O-].CC(C)(C)[O-].CC(C)(C)[O-] GRWPYGBKJYICOO-UHFFFAOYSA-N 0.000 claims description 3
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical compound C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 claims description 3
- 239000007809 chemical reaction catalyst Substances 0.000 claims description 3
- 238000004519 manufacturing process Methods 0.000 claims description 3
- 229930195734 saturated hydrocarbon Natural products 0.000 claims description 3
- 239000004408 titanium dioxide Substances 0.000 claims description 3
- NKFIBMOQAPEKNZ-UHFFFAOYSA-N 5-amino-1h-indole-2-carboxylic acid Chemical compound NC1=CC=C2NC(C(O)=O)=CC2=C1 NKFIBMOQAPEKNZ-UHFFFAOYSA-N 0.000 claims description 2
- 239000002841 Lewis acid Substances 0.000 claims description 2
- 125000002029 aromatic hydrocarbon group Chemical group 0.000 claims description 2
- 150000004945 aromatic hydrocarbons Chemical class 0.000 claims description 2
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 claims description 2
- 125000002091 cationic group Chemical group 0.000 claims description 2
- 125000000959 isobutyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])* 0.000 claims description 2
- 150000007517 lewis acids Chemical group 0.000 claims description 2
- 125000002347 octyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 claims description 2
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 2
- 239000011347 resin Substances 0.000 claims description 2
- 229920005989 resin Polymers 0.000 claims description 2
- 229930195735 unsaturated hydrocarbon Natural products 0.000 claims description 2
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims 4
- 125000004432 carbon atom Chemical group C* 0.000 claims 3
- 125000001183 hydrocarbyl group Chemical group 0.000 claims 3
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 claims 2
- 238000013019 agitation Methods 0.000 claims 1
- 125000005489 p-toluenesulfonic acid group Chemical group 0.000 claims 1
- 229920000642 polymer Polymers 0.000 description 19
- 125000001453 quaternary ammonium group Chemical group 0.000 description 11
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 9
- 239000000376 reactant Substances 0.000 description 8
- -1 amine salt Chemical class 0.000 description 5
- 239000007787 solid Substances 0.000 description 5
- GOLSFPMYASLXJC-UHFFFAOYSA-N 2-(dimethylamino)ethyl acetate Chemical compound CN(C)CCOC(C)=O GOLSFPMYASLXJC-UHFFFAOYSA-N 0.000 description 4
- 239000006260 foam Substances 0.000 description 4
- 239000003999 initiator Substances 0.000 description 4
- 230000008901 benefit Effects 0.000 description 3
- 239000003153 chemical reaction reagent Substances 0.000 description 3
- LGRFSURHDFAFJT-UHFFFAOYSA-N phthalic anhydride Chemical class C1=CC=C2C(=O)OC(=O)C2=C1 LGRFSURHDFAFJT-UHFFFAOYSA-N 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 2
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 2
- 150000001350 alkyl halides Chemical class 0.000 description 2
- JHIWVOJDXOSYLW-UHFFFAOYSA-N butyl 2,2-difluorocyclopropane-1-carboxylate Chemical compound CCCCOC(=O)C1CC1(F)F JHIWVOJDXOSYLW-UHFFFAOYSA-N 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 229910052710 silicon Inorganic materials 0.000 description 2
- 239000010703 silicon Substances 0.000 description 2
- 239000003381 stabilizer Substances 0.000 description 2
- 125000003903 2-propenyl group Chemical group [H]C([*])([H])C([H])=C([H])[H] 0.000 description 1
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 description 1
- 102000006391 Ion Pumps Human genes 0.000 description 1
- 108010083687 Ion Pumps Proteins 0.000 description 1
- 229920005830 Polyurethane Foam Polymers 0.000 description 1
- KXKVLQRXCPHEJC-UHFFFAOYSA-N acetic acid trimethyl ester Natural products COC(C)=O KXKVLQRXCPHEJC-UHFFFAOYSA-N 0.000 description 1
- 230000004913 activation Effects 0.000 description 1
- 125000001931 aliphatic group Chemical group 0.000 description 1
- 150000001338 aliphatic hydrocarbons Chemical class 0.000 description 1
- 125000000217 alkyl group Chemical group 0.000 description 1
- 229920005883 amine-based polyether polyol Polymers 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 229940120638 avastin Drugs 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 238000004821 distillation Methods 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- 238000005187 foaming Methods 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 238000002290 gas chromatography-mass spectrometry Methods 0.000 description 1
- 150000002430 hydrocarbons Chemical group 0.000 description 1
- 230000000977 initiatory effect Effects 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 150000007522 mineralic acids Chemical class 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000002715 modification method Methods 0.000 description 1
- 239000000178 monomer Substances 0.000 description 1
- 230000009965 odorless effect Effects 0.000 description 1
- 239000003921 oil Substances 0.000 description 1
- 235000005985 organic acids Nutrition 0.000 description 1
- 239000011496 polyurethane foam Substances 0.000 description 1
- 150000003254 radicals Chemical class 0.000 description 1
- 239000011541 reaction mixture Substances 0.000 description 1
- 238000004062 sedimentation Methods 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
Classifications
-
- 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
- C08G65/32—Polymers modified by chemical after-treatment
- C08G65/329—Polymers modified by chemical after-treatment with organic compounds
- C08G65/333—Polymers modified by chemical after-treatment with organic compounds containing nitrogen
- C08G65/33396—Polymers modified by chemical after-treatment with organic compounds containing nitrogen having oxygen in addition to nitrogen
-
- 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
- C08G65/32—Polymers modified by chemical after-treatment
- C08G65/329—Polymers modified by chemical after-treatment with organic compounds
- C08G65/337—Polymers modified by chemical after-treatment with organic compounds containing other elements
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/34—Silicon-containing compounds
- C08K3/36—Silica
-
- 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
- C08G2650/00—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule
- C08G2650/02—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule characterized by the type of post-polymerisation functionalisation
- C08G2650/04—End-capping
Landscapes
- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Polyethers (AREA)
Abstract
The invention relates to a preparation method of inorganic modified polyether polyol, which comprises the following steps: firstly, basic polyether polyol reacts with organic acid containing tertiary amine and derivatives thereof under the action of a catalyst to prepare polyether polyol containing tertiary amine groups; then, reacting polyether polyol containing tertiary amine group with halogenated alkane to prepare a quaternary ammonium salt type dispersing agent; and finally, dispersing the inorganic powder material in the basic polyether under the action of a quaternary ammonium salt type dispersing agent to finally prepare the inorganic modified polyether polyol. The prepared polyether polyol has the characteristics of no odor, lower cost, better stability and the like.
Description
Technical Field
The invention relates to a novel preparation method of inorganic modified polyether polyol, in particular to a preparation method of inorganic modified polyether polyol which is odorless and low in cost by using a novel stabilizer as a raw material.
Background
The traditional polymer polyol is also called polymer grafted polyether polyol, and is an important variety of polyol for polyurethane foam, and the polymer polyol is originally developed mainly based on the use in a soft foam formula to improve the load bearing performance of the foam, but the cost is also improved correspondingly compared with the cost of the soft foam polyether.
The main reason why the addition of the polymer polyol improves the load-bearing capacity of the foam is that the solid content of the polymer polyol exists, so that the support performance of the polymer polyol can be effectively improved by improving the solid content of the polymer polyol.
However, the polymer polyol preparation process has a problem which is difficult to completely solve: an unpleasant odor is generated. The reason for this is mainly the decomposition products of the free radical initiator during the synthesis, however, in the aspect of people's life, the products produced by using the polymer polyol are very necessary to reduce or eliminate the odor in the polymer polyol. There is a need to address the odor of polymer polyols by eliminating the odor emitted by initiators and their products.
Chinese patent CN105461913A discloses a method for preparing silicon modified polyol by dispersing silicon element in polyether. The prepared product has more large particles and is easy to settle, and the requirement on the mixing effect in the reaction process is strict.
In addition, as described in patent CN03811632.4, the modified phthalic anhydride method produces a macromonomer, phthalic anhydride and macromolecular polyether are used to prepare phthalic anhydride half ester to prepare a macromonomer, and then the macromonomer is reacted with styrene and acrylonitrile to prepare polymer polyol, which has the problems of high odor and unobvious cost advantage. The above process is still a reactive modification, which entails odor problems, which also requires intensive post-treatment engineering, increasing the preparation costs. The conventional method for preparing polymer polyol also has the problems of unstable viscosity control and large odor.
In view of the odor problem of polymer polyols in the prior art, there is a need for a novel process for preparing polymer polyols which can be used to prepare polymer polyols having a low odor.
Disclosure of Invention
The invention provides a preparation method of inorganic modified polyether polyol, and the obtained modified polyether polyol has the characteristics of low odor and low cost and has better stability. The prepared inorganic modified polyether polyol has the good characteristics of high support performance of the conventional polymer polyol, has lower cost, can replace the polymer polyol, and is used in foaming.
In order to achieve the above purpose, the invention adopts the following technical scheme:
firstly, basic polyether polyol reacts with organic acid containing tertiary amine and derivatives thereof under the action of a catalyst to prepare polyether polyol containing tertiary amine groups; then, reacting polyether polyol containing tertiary amine group with halogenated alkane to prepare a quaternary ammonium salt type dispersing agent; and finally, dispersing an inorganic powder material, preferably the inorganic powder material subjected to alkaline activation, in the basic polyether under the action of a quaternary ammonium salt type dispersing agent to finally prepare the inorganic modified polyether polyol. The reaction formula for preparing the quaternary ammonium salt type dispersant is as follows:
in the present invention, the molecular weight of the base polyether polyol is 500-; the hydroxyl functionality is 1-6, and the preferred functionality is 3-6; the ethylene oxide content in the base polyether polyol is preferably from 2 to 15% by weight.
In the invention, the structural formula of the tertiary amine-containing organic acid and the derivative thereof is as follows:
r is a hydrogen atom or a C1-4 saturated or unsaturated hydrocarbon group, preferably a hydrogen atom or a methyl group;
R1and R2The alkyl group may be the same or different and is C6-C18 aliphatic hydrocarbon group or C6-C18 aromatic hydrocarbon group, preferably phenyl, methyl, ethyl, butyl, isobutyl, linear or branched octyl, allyl, more preferably methyl and ethyl.
In the invention, in the process of preparing the tertiary amine polyether polyol, the reaction temperature is 50-120 ℃, and preferably 80-110 ℃; the reaction time is 1-5h, preferably 2-3 h.
In the present invention, in the preparation of the tertiary amine-based polyether polyol, the reaction catalyst is a lewis acid-based catalyst such as t-butyl titanate, p-toluenesulfonic acid, calcium naphthenate, cationic resin, and various inorganic or organic acids; can be used singly or one or more of them can be selected. As an alternative embodiment, p-toluenesulfonic acid or tert-butyl titanate may be used.
In the invention, the prepared quaternary ammonium polyether polyol can be directly used for the next reaction, and can also be treated and then reacted, wherein the common treatment modes comprise distillation, rectification, adsorption, extraction and other means. Preferably, the reaction mixture is used in the next reaction without further treatment.
In the process of preparing the quaternary ammonium polyether polyol, the molar ratio of the basic polyether polyol to the tertiary amine-containing organic acid and the derivative thereof is 2:1-1:2, preferably 0.9-1.1: 1, and the dosage of the catalyst is 0.1-5 wt%, preferably 0.1-2 wt% of the dosage of the basic polyether.
In the present invention, the alkyl halide is preferably a C1-C18 saturated or unsaturated aliphatic hydrocarbon, or a C6-C18 aromatic hydrocarbon chlorinated or brominated or iodinated compound, preferably a C1-C4 saturated alkane brominated or iodinated compound, and more preferably methyl iodide or ethyl bromide.
In the invention, the molar ratio of the alkyl halide to the tertiary amine-containing organic acid and the derivative thereof is 2:1-1:2, preferably 0.8-1.2: 1.
In the invention, the reaction temperature of the tertiary amine group-containing polyether polyol and the halogenated alkane is 80-150 ℃, preferably 100-130 ℃; the reaction time is 0.5-5h, preferably 1-2 h.
In the invention, in the process of preparing the inorganic modified polyether polyol, the stirring form of the reaction kettle is single-two-blade paddle, single propulsion paddle, single disc turbine, double propulsion paddles, double disc turbine, and upper propulsion paddle of lower disc turbine, wherein the upper propulsion paddle of the lower disc turbine is preferably selected to ensure good mass transfer effect.
In the invention, in the process of preparing the inorganic modified polyether polyol, the adding amount of the inorganic powder material is 10-80 wt%, preferably 20-5wt 0% based on the total amount of the inorganic powder material and the basic polyether polyol; the base polyether polyol is used in an amount of 20 to 90 wt%, preferably 50 to 80 wt%; the amine salt type polyether polyol (dispersant) is added in an amount of 10 to 40% by weight, preferably 20 to 30% by weight, based on the amount of the base polyether.
In the invention, the inorganic powder material is activated alkaline silicon dioxide or alkaline titanium dioxide, and is obtained by treating the silicon dioxide or the titanium dioxide in an alkaline medium, wherein the alkaline silicon dioxide is preferred; for example, it may be Wake chemical company
H15. The particle size of the inorganic powder material is 100-1000nm, preferably 200-500 nm.
In the invention, in the process of preparing the inorganic modified polyether polyol, the reaction temperature is 30-140 ℃, and preferably 80-120 ℃; preferentially adding a quaternary ammonium salt type dispersant into the basic polyether, and stirring for 0.5-2h, preferably 1-1.5 h; and adding an inorganic powder material for 1-6h, preferably 2-4 h.
In the invention, in order to solve the problem of odor of the modified polyether polyol, the polyether polyol is modified by an inorganic method to prepare the inorganic modified polyether polyol with high solid content (47-48 wt%), and the odor of the polymer polyol product mainly comes from an initiator azo compound and a product ester compound produced by decomposing the initiator azo compound. The inorganic modified polyether polyol has no initiation reaction, and the added inorganic substances have no odor problem, so that experiments prove that the odor problem of the prepared polyether polyol can be effectively reduced.
In the invention, the means for improving the inorganic modified polyether polyol is to stably disperse the small-particle-size solid oxide in the polyether polyol by using a novel stabilizer, so that the prepared inorganic modified polyether polyol has better stability, and the cost of the finished inorganic powder is obviously superior, and the cost can be effectively reduced.
The polyether polyol prepared by the inorganic modification method has the advantages of simple reaction process, low requirements on temperature and pressure control and low production cost; there is no pungent odor due to the absence of the use of monomers; and due to the existence of the self-made two-phase dispersing agent, the prepared polyether polyol has good stability, and the layering phenomenon can not occur after standing for 200 hours.
Detailed Description
The invention will now be further illustrated by the following examples, but is not limited thereto.
Raw materials
Some of the starting materials used in the following examples or comparative examples are illustrated below:
all materials referred to in the examples are, without particular mention, chemically pure reagents purchased from the reagent alatin.
Instrument for testing
The residual bill analysis is carried out by GC-MS: gas phase instrument model: agilent 7890-5975C insert XL-MSD with Triple-Axis Detector; a chromatographic column: DB-5MS (30m 0.25mm 0.25 μm); MS parameters: a vacuum pump: turbo pump, ion source: EI, scanning mode: SIM, ion source temperature: at 250 ℃ to obtain a mixture. And (3) viscosity measurement: measured using a Brookfield DV-II + Pro viscometer, using a spindle RV 6. The shear viscosity torque was measured to be 50.
Example 1
Preparing quaternary ammonium polyether polyol: the reaction kettle adopts a lower disc turbine to push the propeller upwards, and basic polyether is added into the reaction kettle
F3135 (produced by Vanhua chemical Co., Ltd., functionality of 3, hydroxyl value of 35, weight average molecular weight of 5000, ethylene oxide content of 14%) and N, N-dimethylamino methyl acetate (avastin reagent) in a molar ratio of 0.95:1, adding 0.5 wt% of p-toluenesulfonic acid catalyst based on polyether polyol, reacting at 90 ℃, and removing water generated by continuously reacting the system with a diaphragm pump during the reaction for 2 h. After the first step of reaction, bromoethane with the molar ratio of 1.05:1 of the basic polyether polyol is directly added, and the quaternary ammonium salt type dispersing agent is obtained after the reaction for 2 hours at the temperature of 100 ℃.
Preparing inorganic modified polyether polyol: and (3) similarly adopting a lower disc turbine upper propelling paddle in the reaction kettle, adding 100g of dispersing agent and 600g of basic polyether polyol into the kettle, reacting at the temperature of 80 ℃, adding 300g of silicon dioxide powder material under the stirring condition, adding for 2h, continuously stirring for 2h after the feeding is finished, and finishing the reaction.
Example 2
Preparing quaternary ammonium polyether polyol: the reaction kettle adopts a lower disc turbine to push the propeller upwards, and the lower disc turbine is added into the reaction kettle
Adding a p-toluenesulfonic acid catalyst with the dosage of 0.5 wt% of the basic polyether polyol into a reactant with the molar ratio of the F3135 to the N, N-dimethylamino ethyl acetate of 0.95:1, reacting at the temperature of 100 ℃, continuously removing water generated by the reaction of the system by using a diaphragm pump during the reaction, and reacting for 2 hours. After the first step of reaction, bromoethane with the molar ratio of 1.05:1 of the basic polyether polyol is directly added, and the quaternary ammonium salt type dispersing agent is obtained after the reaction for 1 hour at the temperature of 100 ℃.
Preparing inorganic modified polyether polyol: and (3) similarly adopting a lower disc turbine upper propelling paddle in the reaction kettle, adding 100g of dispersing agent and 500g of basic polyether polyol into the kettle, reacting at the temperature of 80 ℃, adding 400g of silicon dioxide powder material under the stirring condition, adding for 2h, continuously stirring for 2h after the feeding is finished, and finishing the reaction.
Example 3
Preparing quaternary ammonium polyether polyol: the reaction kettle adopts a lower disc turbine to push the propeller upwards, and the lower disc turbine is added into the reaction kettle
Adding a p-toluenesulfonic acid catalyst with the dosage of 0.5 wt% of the base polyether polyol into a reactant with the molar ratio of the F3135 to the N, N-dimethylaminoethyl acetate of 0.95:1, reacting at the temperature of 110 ℃, continuously removing water generated by the reaction of the system by using a diaphragm pump during the reaction, and reacting for 2 hours. After the first step of reaction, bromoethane with the molar ratio of 1.05:1 of the basic polyether polyol is directly added, and the quaternary ammonium salt type dispersing agent is obtained after the reaction for 1.5 hours at the temperature of 100 ℃.
Preparing inorganic modified polyether polyol: and (3) similarly adopting a lower disc turbine upper propelling paddle in the reaction kettle, adding 100g of dispersing agent and 400g of basic polyether polyol into the kettle, reacting at the temperature of 80 ℃, adding 500g of silicon dioxide powder material under the stirring condition, adding for 2h, continuously stirring for 2h after the feeding is finished, and finishing the reaction.
Example 4
Preparing quaternary ammonium polyether polyol: the reaction kettle adopts a lower disc turbine to push the propeller upwards, and the lower disc turbine is added into the reaction kettle
Adding a p-toluenesulfonic acid catalyst with the dosage of 1 wt% of the basic polyether polyol into a reactant with the molar ratio of the F3135 to the N, N-methyl dimethylaminoacetate of 1:1, reacting at the temperature of 90 ℃, and continuously removing water generated by the reaction of the system by using a diaphragm pump during the reaction, wherein the reaction time is 2 hours. After the first step of reaction, methyl iodide with the molar ratio of 1.03:1 to the basic polyether polyol is directly added, and the quaternary ammonium salt type dispersing agent is obtained after the reaction for 2 hours at 110 ℃.
Preparing inorganic modified polyether polyol: and (3) similarly adopting a lower disc turbine upper propelling paddle in the reaction kettle, adding 130g of dispersing agent and 570g of basic polyether polyol into the kettle, reacting at the temperature of 80 ℃, adding 300g of silicon dioxide powder material under the stirring condition, adding for 2 hours, continuously stirring for 2 hours after the feeding is finished, and finishing the reaction.
Example 5
Preparing quaternary ammonium polyether polyol: the reaction kettle adopts a lower disc turbine to push the propeller upwards, and the lower disc turbine is added into the reaction kettle
Adding a p-toluenesulfonic acid catalyst with the dosage of 1 wt% of the basic polyether polyol into a reactant with the molar ratio of the F3135 to the N, N-dimethylamino ethyl acetate of 1:1, reacting at the temperature of 100 ℃, and continuously removing water generated by the reaction of the system by using a diaphragm pump during the reaction for 2 hours. After the first step of reaction, methyl iodide with the molar ratio of 1.03:1 to the basic polyether polyol is directly added, and the quaternary ammonium salt type dispersing agent is obtained after the reaction for 1 hour at 110 ℃.
Preparing inorganic modified polyether polyol: and (3) similarly adopting a lower disc turbine upper propelling paddle in the reaction kettle, adding 130g of dispersing agent and 470g of basic polyether polyol into the kettle, reacting at the temperature of 80 ℃, adding 400g of silicon dioxide powder material under the stirring condition, adding for 2h, continuously stirring for 2h after the feeding is finished, and finishing the reaction.
Example 6
Preparing quaternary ammonium polyether polyol: the reaction kettle adopts a lower disc turbine to push the propeller upwards, and the lower disc turbine is added into the reaction kettle
Adding a p-toluenesulfonic acid catalyst with the dosage of 1 wt% of the basic polyether polyol into a reactant with the molar ratio of the F3135 to the N, N-methyl dimethylaminoacetate of 1:1, reacting at the temperature of 110 ℃, and continuously removing water generated by the reaction of the system by using a diaphragm pump during the reaction for 2 hours. After the first step of reaction, methyl iodide with the molar ratio of 1.03:1 to the basic polyether polyol is directly added, and the quaternary ammonium salt type dispersing agent is obtained after the reaction for 1.5 hours at 110 ℃.
Preparing inorganic modified polyether polyol: and (3) similarly adopting a lower disc turbine upper propelling paddle in the reaction kettle, adding 130g of dispersing agent and 370g of basic polyether polyol into the kettle, reacting at the temperature of 80 ℃, adding 500g of silicon dioxide powder material under the stirring condition, adding for 2h, continuously stirring for 2h after the feeding is finished, and finishing the reaction.
Example 7
Preparing quaternary ammonium polyether polyol: the reaction kettle adopts a lower disc turbine to push the propeller upwards, and the lower disc turbine is added into the reaction kettle
Adding a p-toluenesulfonic acid catalyst with the dosage of 2 wt% of the base polyether polyol into a reactant with the molar ratio of the F3135 to the N, N-methyl dimethylaminoacetate of 1.05:1, reacting at the temperature of 90 ℃, and continuously removing water generated by the reaction of the system by using a diaphragm pump during the reaction for 2 hours. After the first step of reaction, methyl iodide with the molar ratio of 1.05:1 to the basic polyether polyol is directly added, and the quaternary ammonium salt type dispersing agent is obtained after the reaction for 2 hours at the temperature of 120 ℃.
Preparing inorganic modified polyether polyol: and (3) similarly adopting a lower disc turbine upper propelling paddle in the reaction kettle, adding 150g of dispersing agent and 550g of basic polyether polyol into the kettle, reacting at the temperature of 80 ℃, adding 300g of silicon dioxide powder material under the stirring condition, adding for 2h, continuously stirring for 2h after the feeding is finished, and finishing the reaction.
Example 8
Preparing quaternary ammonium polyether polyol: the reaction kettle adopts a lower disc turbine to push the propeller upwards, and the lower disc turbine is added into the reaction kettle
Adding a p-toluenesulfonic acid catalyst with the dosage of 2 wt% of the basic polyether polyol into a reactant with the molar ratio of the F3135 to the N, N-dimethylamino ethyl acetate of 1.05:1, reacting at the temperature of 100 ℃, continuously removing water generated by the reaction of the system by using a diaphragm pump during the reaction, and reacting for 2 hours. After the first step of reaction, methyl iodide with the molar ratio of 1.05:1 to the basic polyether polyol is directly added, and the quaternary ammonium salt type dispersing agent is obtained after the reaction for 1.5 hours at the temperature of 120 ℃.
Preparing inorganic modified polyether polyol: and (3) similarly adopting a lower disc turbine upper propelling paddle in the reaction kettle, adding 150g of dispersing agent and 4500g of basic polyether polyol into the kettle, reacting at the temperature of 80 ℃, adding 400g of silicon dioxide powder material under the stirring condition, adding for 2h, continuously stirring for 2h after the feeding is finished, and finishing the reaction.
Example 9
Preparing quaternary ammonium polyether polyol: the reaction kettle adopts a lower disc turbine to push the propeller upwards, and the lower disc turbine is added into the reaction kettle
Adding a p-toluenesulfonic acid catalyst with the dosage of 2 wt% of the base polyether polyol into a reactant with the molar ratio of the F3135 to the N, N-methyl dimethylaminoacetate of 1.05:1, reacting at the temperature of 110 ℃, and continuously removing water generated by the reaction of the system by using a diaphragm pump during the reaction for 2 hours. After the first step of reaction, methyl iodide with the molar ratio of 1.05:1 to the basic polyether polyol is directly added, and the quaternary ammonium salt type dispersing agent is obtained after the reaction for 1 hour at the temperature of 100 ℃.
Preparing inorganic modified polyether polyol: and (3) similarly adopting a lower disc turbine upper propelling paddle in the reaction kettle, adding 150g of dispersing agent and 350g of basic polyether polyol into the kettle, reacting at the temperature of 80 ℃, adding 500g of silicon dioxide powder material under the stirring condition, adding for 2h, continuously stirring for 2h after the feeding is finished, and finishing the reaction.
| Example of the implementation | Solid content% | Viscosity of the oil | Stability of 200h |
| 1 | 29.3 | 2489 | √ |
| 2 | 39.1 | 5691 | √ |
| 3 | 47.8 | 6437 | √ |
| 4 | 28.9 | 2786 | √ |
| 5 | 38.7 | 5781 | √ |
| 6 | 47.2 | 6760 | √ |
| 7 | 28.3 | 2911 | √ |
| 8 | 37.5 | 5773 | √ |
| 9 | 47.4 | 6954 | √ |
| Comparative example | 44 | About 5000 of |
And is commercially available
Compared with POP2045 (produced by Wanhua chemical industry), the POP2045 has the advantages of slightly high viscosity, good stability, low cost, no odor and strong superiority. "√" indicates: standing for 200h without demixing or sedimentation.
Claims (22)
1. A method for preparing an inorganic modified polyether polyol, comprising the steps of: firstly, basic polyether polyol reacts with organic acid containing tertiary amine and derivatives thereof under the action of a catalyst to prepare polyether polyol containing tertiary amine groups; then, reacting polyether polyol containing tertiary amine group with halogenated alkane to prepare a quaternary ammonium salt type dispersing agent; finally, dispersing the inorganic powder material in the basic polyether under the action of a quaternary ammonium salt type dispersing agent to finally prepare inorganic modified polyether polyol; the inorganic powder material is alkaline silicon dioxide or alkaline titanium dioxide, and the structural formula of the tertiary amine-containing organic acid and the derivative thereof is as follows:
r is a hydrogen atom or a C1-4 saturated hydrocarbon group or a C2-4 unsaturated hydrocarbon group; r1And R2The same or different, and is a C1-18 saturated hydrocarbon group or a C6-18 aromatic hydrocarbon group.
2. The method of claim 1 wherein the base polyether polyol has a molecular weight of 500-; a hydroxyl functionality of 1 to 6.
3. The method as claimed in claim 2, wherein the molecular weight of the base polyether polyol is 2000-10000; a hydroxyl functionality of 3 to 6; the ethylene oxide content of the base polyether polyol is 2-15 wt%.
4. The process according to claim 1, wherein the tertiary amine-containing organic acid and its derivative have the formula: r is a hydrogen atom or a methyl group; r1And R2Identical or different, phenyl, methyl, ethyl, butyl, isobutyl, linear or branched octyl; and/or the molar ratio of the basic polyether polyol to the tertiary amine-containing organic acid and the derivative thereof is 2:1-1: 2.
5. The method of claim 4, wherein R is1And R2Identical or different, are methyl and ethyl; and/or the molar ratio of the basic polyether polyol to the tertiary amine-containing organic acid and the derivative thereof is 0.9-1.1: 1.
6. The process according to any one of claims 1 to 5, wherein the reaction conditions of the base polyether polyol with the tertiary amine-containing organic acid and its derivative are: the reaction temperature is 50-120 ℃; the reaction time is 1-5 h.
7. The process of claim 6, wherein the reaction conditions of the base polyether polyol with the tertiary amine-containing organic acid and its derivatives are: the reaction temperature is 80-110 ℃; the reaction time is 2-3 h.
8. The process according to any one of claims 1 to 5, wherein in the preparation of the tertiary amine group-containing polyether polyol, the reaction catalyst is a Lewis acid-based catalyst: one or more of tert-butyl titanate, p-toluenesulfonic acid, calcium naphthenate and cationic resin; and/or the amount of the catalyst is 0.1-5 wt% of the amount of the base polyether.
9. The production method according to claim 8, wherein the reaction catalyst is p-toluenesulfonic acid and/or tert-butyl titanate; and/or the amount of the catalyst is 0.5-2 wt% of the amount of the base polyether.
10. The preparation method according to any one of claims 1 to 5, wherein in the preparation of the quaternary ammonium salt dispersant, the halogenated alkane is a chlorinated or brominated or iodinated compound of a saturated alkane with 1 to 18 carbon atoms, an unsaturated alkane with 2 to 18 carbon atoms or an aromatic hydrocarbon with 6 to 18 carbon atoms, and/or the amount of the halogenated alkane is 2:1 to 1: 2;
and/or the reaction temperature of the polyether glycol containing tertiary amine group and the halogenated alkane is 80-150 ℃; the reaction time is 0.5-5 h.
11. The method according to claim 10, wherein the halogenated alkane is a brominated or iodinated compound of a saturated alkane having 1 to 4 carbons; and/or the dosage of the halogenated alkane is 0.8-1.2: 1 of the molar ratio of the halogenated alkane to the tertiary amine-containing organic acid and the derivatives thereof; and/or the reaction temperature of the polyether glycol containing the tertiary amine group and the halogenated alkane is 100-130 ℃; the reaction time is 1-2 h.
12. The method of claim 11, wherein the halogenated alkane is methyl iodide and/or ethyl bromide.
13. The process according to any one of claims 1 to 5, wherein the stirring in the reaction vessel during the preparation of the inorganically modified polyether polyol is carried out in the form of single two-blade paddles, single propeller blades, single disk turbines, double propeller blades, double disk turbines, lower disk turbines and upper propeller blades.
14. The method of claim 13, wherein the reaction vessel agitation is in the form of lower disk turbine upper propeller.
15. The method of claim 13, wherein the inorganic powder material is added in an amount of 10 to 80 wt% based on the total amount of the inorganic powder material and the base polyether polyol; the dosage of the basic polyether polyol is 20-90 wt%; the quaternary ammonium salt dispersant is added in an amount of 10 wt% to 40 wt% based on the amount of the polyether.
16. The method of claim 15, wherein the inorganic powder material is added in an amount of 20 to 50 wt% based on the total amount of the inorganic powder material and the base polyether polyol; the dosage of the basic polyether polyol is 50-80 wt%; the addition amount of the quaternary ammonium salt dispersant is 20-30 wt% of the base polyether.
17. The method of claim 15, wherein the inorganic powder material is alkaline silica; the particle size of the powder material is 100-1000 nm.
18. The method as claimed in claim 17, wherein the particle size of the powder material is 200-500 nm.
19. The process according to any one of claims 1 to 5, wherein the reaction temperature for preparing the inorganic modified polyether polyol is from 30 ℃ to 140 ℃; the adding time of the powder material is 1-6 h.
20. The process according to claim 19, wherein the reaction temperature for preparing the inorganic modified polyether polyol is 80 to 120 ℃; the adding time of the powder material is 2-4 h.
21. The method according to claim 19, wherein the quaternary ammonium salt type dispersant is added to the base polyether and stirred for 0.5 to 2 hours; and adding an inorganic powder material for 1-6 h.
22. The method according to claim 21, wherein the quaternary ammonium salt type dispersant is added to the base polyether and stirred for 1 to 1.5 hours; and adding an inorganic powder material for 2-4 h.
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Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101376707A (en) * | 2008-10-07 | 2009-03-04 | 青岛科技大学 | Method for synthesizing polyether type high polymer quaternary ammonium salt |
| CN102503841A (en) * | 2011-10-08 | 2012-06-20 | 中国日用化学工业研究院 | Ethoxylate ester quaternary ammonium salt and its preparation method |
| CN103897201A (en) * | 2014-04-09 | 2014-07-02 | 东南大学 | Method of preparing quaternary ammonium salt polymer network |
| CN106084203A (en) * | 2016-06-20 | 2016-11-09 | 苏州睿研纳米医学科技有限公司 | A kind of water soluble block polyquaternary ammonium salt macromolecular material and preparation method thereof |
-
2018
- 2018-12-17 CN CN201811540413.3A patent/CN109627434B/en active Active
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101376707A (en) * | 2008-10-07 | 2009-03-04 | 青岛科技大学 | Method for synthesizing polyether type high polymer quaternary ammonium salt |
| CN102503841A (en) * | 2011-10-08 | 2012-06-20 | 中国日用化学工业研究院 | Ethoxylate ester quaternary ammonium salt and its preparation method |
| CN103897201A (en) * | 2014-04-09 | 2014-07-02 | 东南大学 | Method of preparing quaternary ammonium salt polymer network |
| CN106084203A (en) * | 2016-06-20 | 2016-11-09 | 苏州睿研纳米医学科技有限公司 | A kind of water soluble block polyquaternary ammonium salt macromolecular material and preparation method thereof |
Non-Patent Citations (1)
| Title |
|---|
| In vivo biostability of polyurethane-organosilicate nanocomposites;Styan, KE et al.;《ACTA BIOMATERIALIA》;20120731;第8卷(第6期);2243-2253 * |
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