One Method of Producing Polyether Polymer Dispersant and Polyether Polymer

Abstract

The invention discloses one method of producing polyether polymer dispersant and polyether polymer, wherein the dispersant is a copolymer macromolecule prepared by the propylene oxide or ethylene oxide with an average molecular weight of 6000 to 20000, with containing at least one benzene ring group and one polymerizable carbon-carbon double or triple bond polymer. The preparation method of the dispersant is: synthesizing a basic polyether polyol, adding a cyclic dicarboxylic anhydride into the polyether polyol, then the polyether polyol is reacted with an epoxy compound with the polymerizable double bond, and capping with an epoxy compound to obtain the dispersant; preparing the polymer polyol by the basic polyol, an unsaturated vinyl monomer styrene and acrylonitrile, a polymerization initiator, the dispersant and an optional chain transfer agent; the basic polyether is a polyether polyol with a functionality of 3 to 8.

Claims

1. A dispersant for polymer polyol, wherein: the dispersant is a copolymer macromolecule with a weight percentage of 50%-90% of propylene oxide and 0%-20% of ethylene oxide, respectively; the macromolecule has an average molecular weight from 6000 to 20000, with containing at least one benzene ring group and one polymerizable carbon-carbon double or triple bond polymer.

2. A preparation method of the dispersant for polymer polyol according to claim 1 and a preparation method of polymer polyol, wherein: the preparation method of the dispersant is: synthesizing a basic polyether polyol, adding a cyclic dicarboxylic anhydride into the polyether polyol, then the polyether polyol is reacted with a compound with the polymerizable double bond, and capping with an epoxy compound to obtain the dispersant. preparing the polymer polyol at a temperature of 100-130 C. by the basic polyol, an unsaturated vinyl monomer styrene and acrylonitrile, a polymerization initiator, the dispersant and an optional chain transfer agent; the basic polyether is a polyether polyol with a functionality of 3 to 8; the propylene oxide and ethylene oxide are block polymerized, wherein the content of ethylene oxide is 0-50%, and the molecular weight thereof is 5000-20000.

3. The dispersant for polymer polyol and the preparation method of polymer polyol according to claim 2, wherein the initiator of polyether polyol is ethylene glycol, trimethylolpropane, tripropylene glycol, diethylene glycol, glycerin, pentaerythritol, xylitol, sorbitol, sucrose, preferably glycerin, pentaerythritol and sorbitol; the catalyst used for the synthesis of polyether polyol is a potassium hydroxide or bimetallic catalyst.

4. The dispersant for polymer polyol and the preparation method of polymer polyol according to claim 2, wherein the cyclic dicarboxylic anhydride added in the dispersant is maleic anhydride, phthalic anhydride, preferably phthalic anhydride; the mole number of cyclic dicarboxylic anhydride is 0.2-2.0 mol, preferably 0.8-1.5 mol.

5. The dispersant for polymer polyol and the preparation method of polymer polyol according to claim 2, wherein the polymerizable double bond compound is glycidyl methacrylate, methyl methacrylate, allyl glycidyl ether, hydroxypropyl acrylate, methacrylic acid and hydroxyethyl methacrylate, 3-isopropenyl-, -dimethylbenzyl isocyanate, preferably glycidyl methacrylate, allyl glycidyl ether and 3-isopropenyl-, -dimethylbenzyl isocyanate.

6. The dispersant for polymer polyol and the preparation method of polymer polyol according to claim 2, wherein the capping epoxy olefin is selected from one of propylene oxide, ethylene oxide, and butylene oxide.

7. The dispersant for polymer polyol and the preparation method of polymer polyol according to claim 2, wherein the polymerization initiator is an azo compound or a peroxide; the azo compound is azodiisobutyronitrile (AIBN), and the weight of the polymerization initiator is 0.3-0.7% of the total weight.

8. The dispersant for polymer polyol and the preparation method of polymer polyol according to claim 2, wherein the chain transfer agent is isopropanol, dodecyl mercaptan, ethanol, methanol, cyclohexane, toluene, ethylbenzene, tert-butanol, etc., preferably isopropanol, and the weight of the chain transfer agent is 1-10% of the total weight.

9. The dispersant for polymer polyol and the preparation method of polymer polyol according to claim 2, wherein the vinyl monomer is styrene and acrylonitrile with a weight ratio of 80:20-20:80, and the weight of the vinyl monomer is 30-60% of the total weight.

10. A polymer polyol prepared by the preparation method according to claim 2, wherein the polymer polyol is a polymer polyol without by-products.

Description

DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

[0017] The technical solutions of the invention will be described in more detail hereinafter with reference to the specific embodiments.

Embodiment 1: Synthesis of the Dispersant for POP

[0018] Preparation of Polyether Polyol A1

[0019] Adding potassium hydroxide into glycerin with a molecular weight of 92 g/mol, adding propylene oxide to polymerize at a temperature of 115 C., capping with 15 wt % of ethylene oxide to produce trifunctional polyether polyol with a molecular weight of 6000 g/mol; the product is added with water, neutralized with phosphoric acid, adsorbed with refining agent and carclazyte, and filtered to obtain the final product A1, with a hydroxyl value of 28 mgKOH/g.

[0020] Preparation of Polyether Polyol A2

[0021] Adding potassium hydroxide into pentaerythritol with a molecular weight of 136 g/mol, adding the 85/15 mixture of propylene oxide and ethylene oxide to polymerize at a temperature of 115 C. to produce tetrafunctional polyether polyol with a molecular weight of 8000 g/mol; the product is added with water, neutralized with phosphoric acid, adsorbed with refining agent and carclazyte, and filtered to obtain the final product A2, with a hydroxyl value of 28 mgKOH/g.

[0022] Preparation of Polyether Polyol A3

[0023] Adding potassium hydroxide into sorbitol with a molecular weight of 182.17 g/mol, adding propylene oxide to polymerize at a temperature of 115 C. to produce hexafunctional polyether polyol with a hydroxyl value of 210 mgKOH/g; the product is added with water, neutralized with phosphoric acid, adsorbed with refining agent and carclazyte, and filtered to obtain the final product; adding 50 ppm of bimetallic catalyst (Cobalt-zinc double metal cyanide complex catalyst) to the product, and adding the 85/15 mixture of propylene oxide and ethylene oxide to polymerize at a temperature of 130 C. to produce hexafunctional polyether polyol A3, with a molecular weight of 12000 g/mol and a hydroxyl value of 28 mgKOH/g.

Embodiment B1: Preparation of the Dispersant for POP

[0024] Adding a small amount of potassium hydroxide and polyether polyol A1 to the reaction vessel; heating to 110 C. under a low pressure of 0.1 MPa to dehydrate for 1 hour; lowering the temperature to 80 C.; adding phthalic anhydride (PA) into the reaction vessel; replacing the reaction vessel with nitrogen; heating to 110 C. under the protection of nitrogen; after the temperature is raised to 110 C., adding glycidyl methacrylate (GMA) and 3-isopropenyl-, -dimethylbenzyl isocyanate (TMI) into the reaction vessel at this temperature for 4 h, then adding propylene oxide into the reaction vessel and terminating the reaction when the acid value is less than 0.5 mgKOH/g; the obtained product is a colorless and transparent liquid, with a viscosity of 1550 cps/25 C. and an acid value of 0.26 mgKOH/g.

Embodiments B2-B3

[0025] Preparing the dispersant for POP in the same way as in Embodiment B1, but replacing the polyether polyol A1 with A2 and A3, as shown in Table 1.

Embodiment B4

[0026] Preparing the dispersant for POP in the same way as in Embodiment B3, but replacing the glycidyl methacrylate (GMA) with allyl glycidyl ether (AGE), as shown in Table 1.

Embodiments B5-B6

[0027] Preparing the dispersant for POP in the same way as in Embodiment B3, but changing the amounts of GMA and AGE, as shown in Table 1.

TABLE-US-00001 TABLE 1 Embodiments for the Synthesis of Dispersant for POP Polyether GM Polyether Polyol KOH PA A AGE TMI PO Acid Embodiments Polyol (g) (g) (g) (g) (g) (g) (g) Appearance Value Viscosity B1 A1 1000 0.15 23.7 24.7 / 16.7 24.7 Colorless 0.26 1550 and Transparent B2 A2 1000 0.15 17.7 18.5 / 12.5 18.5 Colorless 0.31 1630 and Transparent B3 A3 1000 0.15 11.8 12.3 / 8.4 12.3 Colorless 0.16 1760 and Transparent B4 A3 1000 0.15 11.8 / 9.5 8.4 9.5 Yellowish 0.35 1650 and Transparent B5 A3 1000 0.15 11.8 17.2 / 11.7 17.2 Colorless 0.29 1890 and Transparent B6 A3 1000 0.15 11.8 12.3 / 0 12.3 Yellowish 0.33 1660 and Slight Turbid

Comparative Embodiment (Synthesis of Dispersant for POP; Dispersant E)

[0028] For comparison with the invention, preparing the macromonomers according to the method of patent WO2014055282.

[0029] Preparing the polyol with an OH number of 28 by reacting the sorbitol with an OH functionality of 6 with the propylene oxide and ethylene oxide (12 wt %); adding 0.55 moles of 3-isopropenyl-, -dimethylbenzyl isocyanate (TMI), then adding a very small amount of tin catalyst, and terminating the reaction after 120 minutes of mixing. The product has a viscosity of 1620 cps/25 C., a viscosity of 5310 cps/25 C. after 72 hours, a poor stability, and an appearance of colorless and turbidity.

[0030] It can be seen from the above comparative analysis that the dispersant prepared by the preparation method of the invention has a similar viscosity when compared with the comparative embodiment, but the dispersant prepared by the invention has high transparency without changes after a long-term storage, and is stable.

Embodiment 2: Preparation of Common POP (SP.1)

[0031] Adding 188.8 g of polyol (polyether polyol B with a hydroxyl value of 56.1 mgKOH/g and a functionality of 3) into a 2 liter reactor equipped with a reflux condenser and a stirrer, heating to 120 C. under the protection of nitrogen; when the temperature in the reactor is maintained at 120-125 C., continuously adding the monomer mixture (423.2 g of polyol B, 7.2 g of AIBN, 162 g of acrylonitrile, 378 g of styrene, 48 g of dispersant B 1, and 96 g of isopropanol) into the reactor over 90 minutes. After the addition of the monomer mixture is completed, aging the reaction for 60 minutes, and after the age, degassing under a vacuum of 0.1 MPa for 2 hours to remove unreacted monomers and isopropyl alcohol. The solid content is 44.1%.

Embodiments 3-7: Preparation of Common POP (SP.2-6)

[0032] Preparing the POP in the same way as in Embodiment 2, but the type of dispersant applied is varied, as shown in Table 2.

Embodiment 8: Preparation of High-Activity POP (SP.7)

[0033] Adding 166.6 g of polyol (polyether polyol c with a hydroxyl value of 34 mgKOH/g and a functionality of 3, and is capped with 15 wt % of ethylene oxide) into a 2 liter reactor equipped with a reflux condenser and a stirrer, heating to 120 C. under the protection of nitrogen; when the temperature in the reactor is maintained at 120-125 C., continuously adding the monomer mixture (373.4 g of polyol C, 6 g of AIBN, 140 g of acrylonitrile, 280 g of styrene, 45.4 g of dispersant B1, and 80 g of isopropanol) into the reactor over 90 minutes. After the addition of the monomer mixture is completed, aging the reaction for 60 minutes, and after the age, degassing under a vacuum of 0.1 MPa for 2 hours to remove unreacted monomers and isopropyl alcohol. The solid content is 40.6%.

Embodiments 9-13: Preparation of High-Activity POP (SP.8-12)

[0034] Preparing the POP in the same way as in Embodiment 8, but the type of dispersant applied is varied, as shown in Table 3.

[0035] Comparative Embodiments 2 and 3: preparation of POP: for comparison with the invention, preparing the POP in the same way as in Embodiment 2 and Embodiment 8, but the dispersant used is dispersant E in Comparative Embodiment 1, as shown in Table 2.

TABLE-US-00002 TABLE 2 Embodiments of the Preparation of Common POP Comparative Embodiments SP1 SP2 SP3 SP4 SP5 SP6 Embodiment 2 Polyol B (g) 306 306 306 306 306 306 306 Type of B1 B2 B3 B4 B5 B6 Dispersant E Dispersant Amount of 24 24 24 24 24 24 24 Dispersant (g) Isopropanol (g) 48 48 48 48 48 48 48 Styrene (g) 181 181 181 181 181 181 181 Acrylonitrile (g) 89 89 89 89 89 89 89 AIBN (g) 3.6 3.6 3.6 3.6 3.6 3.6 3.6 Solid Content (%) 44.1 44.2 44.5 44.0 44.7 44.3 44.1 Viscosity 5430 5290 4880 5370 4650 6870 5960 (cps/25 C.) Particles A Few Fine Fine Large Fine Large Large and Large Color and Luster White White White Milky White Milky Milky White White White Viscosity after 5720 5500 5260 5940 4850 7960 7510 Water-Solution (cps/25 C.)

[0036] Note: water-solution test: taking 100 g of POP in a 200 ml beaker, adding 5 g of water at normal temperature, stirring rapidly with a glass rod, and measuring the viscosity of POP.

TABLE-US-00003 TABLE 3 Embodiments of the Preparation of High-active POP Comparative Embodiments SP7 SP8 SP9 SP10 SP11 SP12 Embodiment 3 Polyol C (g) 270 270 270 270 270 270 270 Type of B1 B2 B3 B4 B5 B6 Dispersant E Dispersant Amount of 22.7 22.7 22.7 22.7 22.7 22.7 22.7 Dispersant (g) Isopropanol (g) 40 40 40 40 40 40 40 Styrene (g) 140 140 140 140 140 140 140 Acrylonitrile (g) 70 70 70 70 70 70 70 AIBN (g) 3 3 3 3 3 3 3 Solid Content (%) 40.6 40.5 41.2 40.6 41.4 40.8 40.5 Viscosity 7110 6690 6360 6940 6100 8430 7610 (cps/25 C.) Particles A Few Fine Fine Large Fine Large Large and Large Color and Luster White White White Milky White Milky Milky White White White Viscosity after 8620 8270 8820 8560 7450 10750 10340 Water-Solution (cps/25 C.)

[0037] Note: water-solution test: taking 100 g of POP in a 200 ml beaker, adding 5 g of water at normal temperature, stirring rapidly with a glass rod, and measuring the viscosity of POP.

[0038] It can be seen from the above comparative analysis that the common POP and high-active POP prepared by the preparation method of the invention have not only a relatively low viscosity, but also fine particles, high whiteness and good water solubility.

[0039] It is obvious that the described embodiments are merely particular embodiments of the invention rather than all embodiments. All other embodiments made by those of ordinary skill in the art based on the embodiments of the invention without creative efforts shall all fall within the protection scope of the invention.