CN113583223A - Preparation of castor oil modified polyester polyol for polyurethane terrace - Google Patents
Preparation of castor oil modified polyester polyol for polyurethane terrace Download PDFInfo
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- CN113583223A CN113583223A CN202110953956.3A CN202110953956A CN113583223A CN 113583223 A CN113583223 A CN 113583223A CN 202110953956 A CN202110953956 A CN 202110953956A CN 113583223 A CN113583223 A CN 113583223A
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- Prior art keywords
- castor oil
- modified polyester
- polyester polyol
- oil modified
- acid
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- 239000004359 castor oil Substances 0.000 title claims abstract description 52
- 235000019438 castor oil Nutrition 0.000 title claims abstract description 52
- ZEMPKEQAKRGZGQ-XOQCFJPHSA-N glycerol triricinoleate Natural products CCCCCC[C@@H](O)CC=CCCCCCCCC(=O)OC[C@@H](COC(=O)CCCCCCCC=CC[C@@H](O)CCCCCC)OC(=O)CCCCCCCC=CC[C@H](O)CCCCCC ZEMPKEQAKRGZGQ-XOQCFJPHSA-N 0.000 title claims abstract description 52
- 229920005906 polyester polyol Polymers 0.000 title claims abstract description 31
- 239000004814 polyurethane Substances 0.000 title claims abstract description 17
- 229920002635 polyurethane Polymers 0.000 title claims abstract description 17
- 238000002360 preparation method Methods 0.000 title claims abstract description 14
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims abstract description 32
- 229920005862 polyol Polymers 0.000 claims abstract description 19
- 150000003077 polyols Chemical class 0.000 claims abstract description 19
- 238000001816 cooling Methods 0.000 claims abstract description 17
- 229910052757 nitrogen Inorganic materials 0.000 claims abstract description 16
- 238000006243 chemical reaction Methods 0.000 claims abstract description 13
- 238000003756 stirring Methods 0.000 claims abstract description 13
- 238000010438 heat treatment Methods 0.000 claims abstract description 11
- 238000000034 method Methods 0.000 claims abstract description 11
- 239000003054 catalyst Substances 0.000 claims abstract description 6
- 150000007519 polyprotic acids Polymers 0.000 claims abstract description 5
- 238000002156 mixing Methods 0.000 claims abstract description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 18
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 claims description 18
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 claims description 18
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 14
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 claims description 12
- 239000002253 acid Substances 0.000 claims description 10
- WNLRTRBMVRJNCN-UHFFFAOYSA-N adipic acid Chemical compound OC(=O)CCCCC(O)=O WNLRTRBMVRJNCN-UHFFFAOYSA-N 0.000 claims description 10
- YHWCPXVTRSHPNY-UHFFFAOYSA-N butan-1-olate;titanium(4+) Chemical compound [Ti+4].CCCC[O-].CCCC[O-].CCCC[O-].CCCC[O-] YHWCPXVTRSHPNY-UHFFFAOYSA-N 0.000 claims description 9
- LGRFSURHDFAFJT-UHFFFAOYSA-N Phthalic anhydride Natural products C1=CC=C2C(=O)OC(=O)C2=C1 LGRFSURHDFAFJT-UHFFFAOYSA-N 0.000 claims description 6
- JHIWVOJDXOSYLW-UHFFFAOYSA-N butyl 2,2-difluorocyclopropane-1-carboxylate Chemical compound CCCCOC(=O)C1CC1(F)F JHIWVOJDXOSYLW-UHFFFAOYSA-N 0.000 claims description 6
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 claims description 6
- 235000004443 Ricinus communis Nutrition 0.000 claims description 5
- 239000001361 adipic acid Substances 0.000 claims description 5
- 235000011037 adipic acid Nutrition 0.000 claims description 5
- WXZMFSXDPGVJKK-UHFFFAOYSA-N pentaerythritol Chemical compound OCC(CO)(CO)CO WXZMFSXDPGVJKK-UHFFFAOYSA-N 0.000 claims description 5
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 4
- KDYFGRWQOYBRFD-UHFFFAOYSA-N Succinic acid Natural products OC(=O)CCC(O)=O KDYFGRWQOYBRFD-UHFFFAOYSA-N 0.000 claims description 4
- KKEYFWRCBNTPAC-UHFFFAOYSA-N Terephthalic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-N 0.000 claims description 4
- ZJCCRDAZUWHFQH-UHFFFAOYSA-N Trimethylolpropane Chemical compound CCC(CO)(CO)CO ZJCCRDAZUWHFQH-UHFFFAOYSA-N 0.000 claims description 4
- 239000003513 alkali Substances 0.000 claims description 4
- WPYMKLBDIGXBTP-UHFFFAOYSA-N benzoic acid Chemical compound OC(=O)C1=CC=CC=C1 WPYMKLBDIGXBTP-UHFFFAOYSA-N 0.000 claims description 4
- WERYXYBDKMZEQL-UHFFFAOYSA-N butane-1,4-diol Chemical compound OCCCCO WERYXYBDKMZEQL-UHFFFAOYSA-N 0.000 claims description 4
- KDYFGRWQOYBRFD-NUQCWPJISA-N butanedioic acid Chemical compound O[14C](=O)CC[14C](O)=O KDYFGRWQOYBRFD-NUQCWPJISA-N 0.000 claims description 4
- 238000005886 esterification reaction Methods 0.000 claims description 4
- QQVIHTHCMHWDBS-UHFFFAOYSA-N isophthalic acid Chemical compound OC(=O)C1=CC=CC(C(O)=O)=C1 QQVIHTHCMHWDBS-UHFFFAOYSA-N 0.000 claims description 4
- VXUYXOFXAQZZMF-UHFFFAOYSA-N titanium(IV) isopropoxide Chemical compound CC(C)O[Ti](OC(C)C)(OC(C)C)OC(C)C VXUYXOFXAQZZMF-UHFFFAOYSA-N 0.000 claims description 4
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims description 3
- 235000011114 ammonium hydroxide Nutrition 0.000 claims description 3
- 230000032050 esterification Effects 0.000 claims description 3
- 150000005846 sugar alcohols Polymers 0.000 claims description 3
- -1 titanate ester Chemical class 0.000 claims description 3
- 239000005711 Benzoic acid Substances 0.000 claims description 2
- GSEJCLTVZPLZKY-UHFFFAOYSA-N Triethanolamine Chemical compound OCCN(CCO)CCO GSEJCLTVZPLZKY-UHFFFAOYSA-N 0.000 claims description 2
- 235000010233 benzoic acid Nutrition 0.000 claims description 2
- JRBPAEWTRLWTQC-UHFFFAOYSA-N dodecylamine Chemical compound CCCCCCCCCCCCN JRBPAEWTRLWTQC-UHFFFAOYSA-N 0.000 claims description 2
- XXMIOPMDWAUFGU-UHFFFAOYSA-N hexane-1,6-diol Chemical compound OCCCCCCO XXMIOPMDWAUFGU-UHFFFAOYSA-N 0.000 claims description 2
- 229910044991 metal oxide Inorganic materials 0.000 claims description 2
- 150000004706 metal oxides Chemical class 0.000 claims description 2
- YOURXVGYNVXQKT-UHFFFAOYSA-N oxacycloundecane-2,11-dione Chemical compound O=C1CCCCCCCCC(=O)O1 YOURXVGYNVXQKT-UHFFFAOYSA-N 0.000 claims description 2
- 230000001105 regulatory effect Effects 0.000 claims description 2
- ZIBGPFATKBEMQZ-UHFFFAOYSA-N triethylene glycol Chemical compound OCCOCCOCCO ZIBGPFATKBEMQZ-UHFFFAOYSA-N 0.000 claims description 2
- SRPWOOOHEPICQU-UHFFFAOYSA-N trimellitic anhydride Chemical compound OC(=O)C1=CC=C2C(=O)OC(=O)C2=C1 SRPWOOOHEPICQU-UHFFFAOYSA-N 0.000 claims description 2
- WATWJIUSRGPENY-UHFFFAOYSA-N antimony atom Chemical compound [Sb] WATWJIUSRGPENY-UHFFFAOYSA-N 0.000 claims 1
- 150000002642 lithium compounds Chemical class 0.000 claims 1
- 150000003606 tin compounds Chemical class 0.000 claims 1
- 150000003609 titanium compounds Chemical class 0.000 claims 1
- 150000003752 zinc compounds Chemical class 0.000 claims 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 abstract description 8
- 239000011527 polyurethane coating Substances 0.000 abstract description 3
- 238000004945 emulsification Methods 0.000 abstract description 2
- 239000004570 mortar (masonry) Substances 0.000 abstract description 2
- 239000011541 reaction mixture Substances 0.000 abstract 1
- 239000000839 emulsion Substances 0.000 description 16
- 150000001875 compounds Chemical class 0.000 description 5
- 239000003995 emulsifying agent Substances 0.000 description 5
- 239000007788 liquid Substances 0.000 description 5
- 239000002994 raw material Substances 0.000 description 5
- 230000000694 effects Effects 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 239000007787 solid Substances 0.000 description 3
- 239000002585 base Substances 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 239000004530 micro-emulsion Substances 0.000 description 2
- PTBDIHRZYDMNKB-UHFFFAOYSA-N 2,2-Bis(hydroxymethyl)propionic acid Chemical compound OCC(C)(CO)C(O)=O PTBDIHRZYDMNKB-UHFFFAOYSA-N 0.000 description 1
- 239000004721 Polyphenylene oxide Substances 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000003245 coal Substances 0.000 description 1
- 150000002148 esters Chemical group 0.000 description 1
- 238000009472 formulation Methods 0.000 description 1
- 238000007710 freezing Methods 0.000 description 1
- 230000008014 freezing Effects 0.000 description 1
- 125000005456 glyceride group Chemical group 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 239000012948 isocyanate Substances 0.000 description 1
- 150000002513 isocyanates Chemical class 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- 229920000570 polyether Polymers 0.000 description 1
- 239000002861 polymer material Substances 0.000 description 1
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 1
- 239000004810 polytetrafluoroethylene Substances 0.000 description 1
- 238000004382 potting Methods 0.000 description 1
- 235000015112 vegetable and seed oil Nutrition 0.000 description 1
- 239000008158 vegetable oil Substances 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
- C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
- C08G63/02—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds
- C08G63/12—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds derived from polycarboxylic acids and polyhydroxy compounds
- C08G63/52—Polycarboxylic acids or polyhydroxy compounds in which at least one of the two components contains aliphatic unsaturation
-
- 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
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/67—Unsaturated compounds having active hydrogen
- C08G18/68—Unsaturated polyesters
-
- 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
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/67—Unsaturated compounds having active hydrogen
- C08G18/68—Unsaturated polyesters
- C08G18/683—Unsaturated polyesters containing cyclic 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
- C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
- C08G63/02—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds
- C08G63/12—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds derived from polycarboxylic acids and polyhydroxy compounds
- C08G63/46—Polyesters chemically modified by esterification
- C08G63/48—Polyesters chemically modified by esterification by unsaturated higher fatty oils or their acids; by resin acids
-
- 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
- C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
- C08G63/66—Polyesters containing oxygen in the form of ether groups
- C08G63/668—Polyesters containing oxygen in the form of ether groups derived from polycarboxylic acids and polyhydroxy compounds
- C08G63/672—Dicarboxylic acids and dihydroxy compounds
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D175/00—Coating compositions based on polyureas or polyurethanes; Coating compositions based on derivatives of such polymers
- C09D175/04—Polyurethanes
- C09D175/14—Polyurethanes having carbon-to-carbon unsaturated bonds
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Polymers & Plastics (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Materials Engineering (AREA)
- Wood Science & Technology (AREA)
- Engineering & Computer Science (AREA)
- Life Sciences & Earth Sciences (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- General Chemical & Material Sciences (AREA)
- Polyurethanes Or Polyureas (AREA)
Abstract
The invention discloses a preparation method of castor oil modified polyester polyol for a polyurethane terrace, which comprises the following steps: the first step is as follows: mixing castor oil and polyol according to a designed proportion, stirring, adding a catalyst under the protection of nitrogen, slowly heating to 160-250 ℃, and keeping the temperature for reaction for 1-4 hours; the second step is that: cooling the product in the first step to 120-160 ℃, adding polybasic acid under the protection of nitrogen, slowly heating to 180-230 ℃, and keeping the temperature for reaction for 4-10 h; after the reaction was completed, the reaction mixture was cooled to room temperature. The aqueous castor oil modified polyester polyol prepared by the method has the advantages of low cost, simple operation process and easy control of reaction, and the product can be directly mixed with water for emulsification without post-treatment, and is applied to the fields of polyurethane coatings and mortar.
Description
Technical Field
The invention belongs to the field of waterborne polyurethane raw materials, and particularly relates to preparation of castor oil modified polyester polyol for a polyurethane terrace.
Background
Polyurethane is a polymer material with wide application, and the main raw materials for production comprise isocyanate, polyol and related additives, wherein the consumption of the polyol accounts for more than half of the raw materials, and the property of the polyol directly determines the performance of the later-stage polyurethane material.
The polyols used in industrial production at present are polyether polyols and polyester polyols, which are mainly derived from non-renewable resources such as petroleum, coal and the like, and with the increasing global energy crisis, it is one of the important directions in the scientific research field to replace the traditional fossil resources with plant resources, wherein castor oil is used as vegetable oil, is a glyceride with a longer fatty chain and secondary hydroxyl groups (average functionality is 2.7, hydroxyl value is 163 mgKOH/g), is a natural polyol raw material, has the characteristics of high ignition point, low freezing point, good stability, good water resistance, excellent low temperature property and excellent electrical property, and the polyurethane material prepared from castor oil has good flexibility, thermal stability and water resistance, and is often used for polyurethane coatings, adhesives, potting materials and the like.
However, the castor oil polyol has higher hydrophobicity due to a longer fatty chain, so that in industrial application, uniform and stable castor oil polyol emulsion is difficult to prepare, a large amount of emulsifier is required to be added, and the product quality is influenced, so that the method for preparing the water-soluble castor oil-based polyol mainly considers 3 aspects: ester exchange, esterification reaction and ionization treatment.
Disclosure of Invention
Aiming at the problems in the prior art, the invention provides a preparation method of castor oil modified polyester polyol for a polyurethane terrace, the current castor oil is mostly directly emulsified by adopting an emulsifier to prepare emulsion in the field of aqueous polyurethane, or micromolecules (such as 2, 2-dimethylolpropionic acid) are adopted to participate in esterification and then are subjected to ionization treatment to prepare the emulsion, the emulsion prepared by the emulsifier has poor stability, the addition amount of the emulsifier is large, and the use of the product is influenced; the aqueous castor oil polyol microemulsion can be prepared by the aqueous castor oil polyol microemulsion, but the emulsion has low solid content, complex preparation process and high cost, and in some fields, the emulsion needing the aqueous castor oil modified polyol has high solid content (more than 70 percent of solid content) and stable emulsion, so the invention mainly aims to prepare the aqueous castor oil polyol for preparing high-solid-content emulsion.
The invention is realized in such a way that the preparation of the castor oil modified polyester polyol for the polyurethane terrace comprises the following steps:
the first step is as follows: mixing castor oil and polyol according to a designed proportion, stirring, adding a catalyst under the protection of nitrogen, slowly heating to 160-250 ℃, and keeping the temperature for reaction for 1-4 hours;
the second step is that: cooling the product in the first step to 120-160 ℃, adding polybasic acid under the protection of nitrogen, slowly heating to 180-230 ℃, and keeping the temperature for reaction for 4-10 h; cooling to room temperature after the reaction is finished;
the third step: adding alkali into the second step according to a designed proportion, reacting at room temperature for 10-60min, and cooling to room temperature after the reaction is finished to obtain the target aqueous castor oil modified polyol.
As preferred in the present invention, the catalyst may be a metal oxide, an organolithiated compound, an organozincated compound, an organoantimonated compound, an organotin compound, an organotitanate compound, etc., preferably a titanate ester such as tetrabutyl titanate, tetraisopropyl titanate, more preferably tetrabutyl titanate, in an amount of 0.01% to 3%, preferably 0.01% to 0.1% of the total amount of the aqueous castor oil-modified polyester polyol.
As preferred in the present invention, the polyhydric alcohol may be 1, 4-butanediol, glycerol, 1, 6-hexanediol, diethylene glycol, triethylene glycol, pentaerythritol, trimethylolpropane, PPG-200, PPG-400, etc., preferably trimethylolpropane, diethylene glycol, pentaerythritol, in an amount of 2 to 20%, preferably 3 to 10%, based on the total amount of the aqueous castor oil-modified polyester polyol.
Preferably, the polybasic acid may be sebacic anhydride, adipic acid, succinic acid, maleic anhydride, phthalic anhydride, isophthalic acid, terephthalic acid, benzoic acid, 4-carboxyphthalic anhydride, and the like, preferably adipic acid, succinic acid, maleic anhydride, and the like, in an amount of 2% to 10%, preferably 2% to 5%, of the total amount of the aqueous castor oil-modified polyester polyol.
Preferably, the base can be triethanolamine, NaOH, KOH, triethylamine, laurylamine, ammonia water, and the like, preferably triethylamine and NaOH, and the amount of the base is 0.1 to 1 percent, preferably 0.1 to 0.4 percent of the total amount of the aqueous castor oil modified polyester polyol.
Preferably, the castor oil polyol has a hydroxyl value of 150-240mgKOH/g, a viscosity of 500-2000mPa · s and an acid value of less than 2.0mgKOH/g, the hydroxyl value and the viscosity of the fed product can be regulated and controlled through formula design according to needs, the hydroxyl value is measured according to a GB/T12008.3-2009 phthalic anhydride esterification method, the acid value is measured according to a GB/T12008.5-2010 method, and the viscosity is measured at 25 ℃ by a rotational viscometer (the specific values are shown in Table I).
The first table is a product effect real-time case table of the formula class;
compared with the prior art, the invention has the following beneficial effects:
1. the aqueous castor oil modified polyester polyol prepared by the method has the advantages of low cost, simple operation process and easy control of reaction, and the product can be directly mixed with water for emulsification without post-treatment, and is applied to the fields of polyurethane coatings and mortar.
2. The product effect of the formula of the invention is that the aqueous castor oil modified polyester polyol with different viscosity and hydroxyl value combinations can be prepared according to the adjustment of the formula raw material system, and the prepared product has low acid value, is easy to neutralize and is easy to ionize.
3. The method has the advantages that the preparation process is simple, the product is easy to emulsify, the product can be mixed with water according to the proportion of 7:3-8:2 without adding any emulsifier, the prepared high-solid-content water emulsion has excellent emulsion stability, and the emulsion is not separated after 30 days, so that the emulsion has excellent emulsion stability.
Detailed Description
In order to further understand the contents, features and effects of the present invention, the following examples are given below.
The structure of the present invention will be described in detail below.
Example 1:
500g of castor oil and 40g of glycerol are added into a 1000mL three-necked bottle; stirring for 30min under the protection of nitrogen at normal temperature, adding 0.35g of tetrabutyl titanate, heating to 230 ℃, and preserving heat for 2h at 230 ℃; cooling to 160 ℃, adding 30g of maleic anhydride, reacting for 5h at 200 ℃, closing nitrogen, cooling to room temperature, adding 1g of NaOH, and stirring to obtain the product of castor oil, wherein the product is light yellow liquid, the viscosity is 1450mPa & s, the hydroxyl value is 210mgKOH/g, and the acid value is 1.5 mgKOH/g.
Example 2:
500g of castor oil and 41g of pentaerythritol are added into a 1000mL three-necked bottle; stirring for 30min under the protection of nitrogen at normal temperature, adding 0.5g of tetrabutyl titanate, heating to 230 ℃, and preserving heat for 1.5h at 230 ℃; cooling to 170 ℃, adding 30g of maleic anhydride, reacting for 4h at 200 ℃, closing nitrogen, cooling to room temperature, adding 1g of triethylamine, and stirring to obtain the product castor oil, wherein the product is light yellow liquid, the viscosity is 1900mPa & s, the hydroxyl value is 200mgKOH/g, and the acid value is 1.0 mgKOH/g.
Example 3:
500g of castor oil and 60g of diethylene glycol are added into a 1000mL three-necked bottle; stirring for 30min under the protection of nitrogen at normal temperature, adding 0.35g of tetrabutyl titanate, heating to 230 ℃, and preserving heat for 3h at 230 ℃; cooling to 160 ℃, adding 40g of phthalic anhydride, reacting for 6h at 200 ℃, closing nitrogen, cooling to room temperature, adding 1.5g of NaOH, and stirring to obtain the product castor oil, wherein the product is light yellow liquid, the viscosity is 850mPa & s, the hydroxyl value is 190mgKOH/g, and the acid value is 1.7 mgKOH/g.
Example 4:
500g of castor oil and 40g of diethylene glycol are added into a 1000mL three-necked bottle; stirring for 30min under the protection of nitrogen at normal temperature, adding 0.2g of tetrabutyl titanate, heating to 230 ℃, and preserving heat for 5h at 230 ℃; cooling to 170 ℃, adding 40g of phthalic anhydride, reacting for 6h at 200 ℃, closing nitrogen, cooling to room temperature, adding 1.5g of triethylamine, and stirring to obtain the product castor oil, wherein the product is light yellow liquid, the viscosity is 1200mPa & s, the hydroxyl value is 160mgKOH/g, and the acid value is 1.5 mgKOH/g.
Example 5:
500g of castor oil and 50g of glycerol are added into a 1000mL three-necked bottle; stirring for 30min under the protection of nitrogen at normal temperature, adding 0.2g of tetrabutyl titanate, heating to 230 ℃, and preserving heat for 4h at 230 ℃; cooling to 160 ℃, adding 50g of adipic acid, reacting for 8h at 220 ℃, closing nitrogen, cooling to room temperature, adding 1g of ammonia water, and stirring to obtain the product castor oil, wherein the product is light yellow liquid, the viscosity is 1750mPa & s, the hydroxyl value is 170mgKOH/g, and the acid value is 1.2 mgKOH/g.
Application example 1:
an emulsion was prepared using the aqueous castor oil-modified polyester polyol obtained in example 1, and then the specific formulation was: 20g of water-based castor oil modified polyester polyol and 8g of water are mixed into emulsion and 20g of modified MDI, the emulsion and the modified MDI are uniformly stirred and then coated on a dried polytetrafluoroethylene board, the constant temperature is kept at 30 ℃ for 3 days, and the specific properties are measured according to the national standard GB/T19250-2013: surface drying time is 6 h; the actual drying time is 24 h; hardness 55D; the tensile strength is 7.3 MPa; the comprehensive performance is extremely excellent.
Claims (6)
1. The preparation method of the castor oil modified polyester polyol for the polyurethane terrace is characterized by comprising the following steps of: the method comprises the following steps:
the first step is as follows: mixing castor oil and polyol according to a designed proportion, stirring, adding a catalyst under the protection of nitrogen, slowly heating to 160-250 ℃, and keeping the temperature for reaction for 1-4 hours;
the second step is that: cooling the product in the first step to 120-160 ℃, adding polybasic acid under the protection of nitrogen, slowly heating to 180-230 ℃, and keeping the temperature for reaction for 4-10 h; cooling to room temperature after the reaction is finished;
the third step: adding alkali into the second step according to a designed proportion, reacting at room temperature for 10-60min, and cooling to room temperature after the reaction is finished to obtain the target aqueous castor oil modified polyol.
2. The preparation method of the castor oil modified polyester polyol for the polyurethane floor as claimed in claim 1, wherein the castor oil modified polyester polyol comprises the following steps: the catalyst can be metal oxide, organic lithium compound, organic zinc compound, organic antimonide, organic tin compound, organic titanium compound, etc., preferably titanate ester, such as tetrabutyl titanate, tetraisopropyl titanate, more preferably tetrabutyl titanate, and the amount of the catalyst is 0.01-3%, preferably 0.01-0.1% of the total amount of the aqueous castor oil modified polyester polyol.
3. The preparation method of the castor oil modified polyester polyol for the polyurethane floor as claimed in claim 1, wherein the castor oil modified polyester polyol comprises the following steps: the polyhydric alcohol may be 1, 4-butanediol, glycerol, 1, 6-hexanediol, diethylene glycol, triethylene glycol, pentaerythritol, trimethylolpropane, PPG-200, PPG-400, etc., preferably trimethylolpropane, diethylene glycol, pentaerythritol, in an amount of 2 to 20%, preferably 3 to 10%, based on the total amount of the aqueous castor oil-modified polyester polyol.
4. The preparation method of the castor oil modified polyester polyol for the polyurethane floor as claimed in claim 1, wherein the castor oil modified polyester polyol comprises the following steps: the polybasic acid can be sebacic anhydride, adipic acid, succinic acid, maleic anhydride, phthalic anhydride, isophthalic acid, terephthalic acid, benzoic acid, 4-carboxyphthalic anhydride and the like, preferably adipic acid, succinic acid, maleic anhydride and the like, and is used in an amount of 2-10%, preferably 2-5% of the total amount of the aqueous castor oil modified polyester polyol.
5. The preparation method of the castor oil modified polyester polyol for the polyurethane floor as claimed in claim 1, wherein the castor oil modified polyester polyol comprises the following steps: the alkali can be triethanolamine, NaOH, KOH, triethylamine, laurylamine, ammonia water and the like, preferably triethylamine and NaOH, and the amount of the alkali is 0.1-1%, preferably 0.1-0.4% of the total amount of the aqueous castor oil modified polyester polyol.
6. The preparation method of the castor oil modified polyester polyol for the polyurethane floor as claimed in claim 1, wherein the castor oil modified polyester polyol comprises the following steps: the castor oil polyhydric alcohol has a hydroxyl value of 150-240mgKOH/g, viscosity of 500-2000mPa & s and an acid value of less than 2.0mgKOH/g, the hydroxyl value and the viscosity of a fed product can be regulated and controlled through formula design according to needs, the hydroxyl value is determined according to a GB/T12008.3-2009 phthalic anhydride esterification method, the acid value is determined according to a GB/T12008.5-2010 method, and the viscosity is determined by a rotational viscometer at 25 ℃.
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| CN115157807A (en) * | 2021-12-31 | 2022-10-11 | 无锡上美纸制品有限公司 | Self-adhesive film for stainless steel and preparation method thereof |
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