Silane-terminated polyester polyols, methods of making and uses thereof
A one-step polycondensation reaction of tribromophenylepoxysilane and polyester polyol was used to prepare silane-terminated polyester polyol, which solved the problems of complex synthesis and poor activity of silane-terminated polyol in the prior art and improved the performance of adhesives.
Patent Information
- Authority / Receiving Office
- CN · China
- Patent Type
- Patents(China)
- Current Assignee / Owner
- WANHUA CHEM GRP CO LTD
- Filing Date
- 2023-08-23
- Publication Date
- 2026-05-19
AI Technical Summary
Existing silane-terminated polyol synthesis processes are complex, have long reaction cycles, and exhibit poor silane activity, resulting in insufficient adhesive performance.
Silane-terminated polyester polyols were prepared by a one-step polycondensation reaction of tribromophenylepoxysilane and polyester polyols, thereby enhancing the activity of silane groups.
The reaction process has been simplified, production efficiency has been improved, and the adhesive has higher bonding performance and strength.
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Abstract
Description
Technical Field
[0001] This invention relates to the field of polyols, and more particularly to a method for preparing a silane-terminated polyester polyol, which can be applied to the field of adhesives. Background Technology
[0002] Polyester polyols are polyol products whose main molecular chain contains repeating ester groups. They are mainly used in the polyurethane field. As a soft segment application, polyester polyol products can effectively improve the mechanical properties of polyurethane products.
[0003] Silane-terminated polyester polyols can be applied in the field of polyurethane adhesives. Because of the silane end-capping, the downstream products have excellent surface properties of silicon modification. During the application process, fewer bubbles are produced, and adhesives made from them have high bonding performance and high strength. The strength performance of these adhesives far exceeds that of existing polyester polyol-based adhesives.
[0004] Existing silane-terminated polyols are mostly based on self-produced polyether polyols. Double bond groups are introduced, followed by hydrosilylation reactions to obtain the desired silane-modified polyol. JP59267 (1993) reported a method for synthesizing adhesives from silane-terminated polyethers. The process involves first synthesizing a high molecular weight double-bonded polyether, then introducing silane under catalytic conditions, followed by an addition reaction to introduce siloxane groups, thus obtaining the silane-terminated modified polyether. This polyether is then used as a raw material to synthesize adhesives. However, this method involves many reaction steps, a long reaction cycle, and relatively poor silane reactivity. Summary of the Invention
[0005] The purpose of this invention is to provide a silane-terminated polyester polyol that, by introducing tribromophenylepoxysilane, can effectively enhance the activity of the silane groups in the product, thereby giving the product higher reactivity.
[0006] Another objective of this invention is to provide a method for preparing the silane-terminated polyester polyol, which uses the polyester polyol as the base polyol and reacts with tribromophenylepoxysilane in a one-step process, thereby greatly improving the reaction efficiency and significantly enhancing the product performance.
[0007] To achieve the above objectives, the technical solution adopted by the present invention is as follows:
[0008] On one hand, the present invention provides a silane-terminated polyester polyol, which is obtained by polycondensation reaction of raw materials containing tribromophenylepoxysilane, small molecule diol and small molecule diacid in the presence of a catalyst.
[0009] In this invention, based on the total mass of raw materials as 100%, the proportions of each substance are as follows:
[0010] Small molecule dicarboxylic acids, 33-65%, preferably 35-50%;
[0011] Small molecule diols 30-60%, preferably 35-55%;
[0012] 5-30% tribromophenylepoxysilane, preferably 10-25%.
[0013] In this invention, the amount of catalyst used is not particularly limited and can be conventionally selected, preferably 50-200 ppm of the total mass of the raw materials, more preferably 50-100 ppm.
[0014] In this invention, the catalyst is selected from one or more of tetrabutyl titanate, isopropyl titanate, stannous octoate, triethylamine octoate, tripropylamine, and p-toluenesulfonic acid, preferably isopropyl titanate.
[0015] In this invention, the tribromophenylepoxysilane is selected from one or more of 2-(3,4-epoxytribromophenyl)ethyltriethoxysilane, 2-(3,4-epoxytribromophenyl)ethyltrimethoxysilane, 3-glycidyl ether(2-tribromophenyl)propyltrimethoxysilane, and 3-glycidyl ether(2-tribromophenyl)propyltriethoxysilane, preferably 2-(3,4-epoxytribromophenyl)ethyltrimethoxysilane.
[0016] In this invention, the small molecule diol is selected from diols with 2-8 carbon atoms, specifically from one or more of ethylene glycol, 1,3-propanediol, 1,4-butanediol, 1,5-pentanediol, diethylene glycol, triethylene glycol, 1,2-propanediol, dipropylene glycol, 2-methyl-2,4-pentanediol, and 3-methyl-1,5-pentanediol, preferably one or more of diethylene glycol or triethylene glycol.
[0017] In this invention, the small molecule dicarboxylic acid is selected from dicarboxylic acids with 4-10 carbon atoms, specifically one or two of succinic acid, adipic acid, heptanoic acid, azelaic acid, terephthalic acid, and isophthalic acid, with adipic acid being preferred.
[0018] On the other hand, the present invention also provides a method for preparing the silane-terminated polyester polyol, the method comprising:
[0019] In an inert atmosphere, a dicarboxylic acid and a diol are first added to carry out the first step of esterification reaction. When the acid value decreases to 10-60 mg KOH / g, preferably 30-40 mg KOH / g, tribromophenylepoxysilane is added, and the reaction is stopped when the acid value decreases to 3 mg KOH / g.
[0020] In this invention, the method is an intermittent process, and the reactor is not particularly limited, but a batch reactor with a self-priming stirring paddle is preferred.
[0021] In this invention, the reaction temperature during the intermittent process is 150-250℃, preferably 160-200℃.
[0022] In this invention, the first step of esterification reaction takes 5-15 hours, preferably 6-8 hours.
[0023] In this invention, after adding epoxy silane in the second step, the reaction time is 5-10 hours, preferably 6-9 hours.
[0024] Finally, the present invention provides the application of the silane-terminated polyester polyol in adhesives, wherein the adhesive comprises the following components in parts by weight:
[0025]
[0026] In this invention, the filler is selected from one or more of titanium dioxide, calcium carbonate, clay, and quartz powder.
[0027] In this invention, the dehydrating agent is selected from one or more of WD-21 and CR-800.
[0028] In this invention, the catalyst is selected from one or more of organotin, tertiary amines, and organobismuth.
[0029] In this invention, the plasticizer is selected from one or more of dioctyl phthalate, dioctyl sebacate, and dibutyl phthalate.
[0030] In this invention, the whitening agent is selected from one or more of WN1701 and KSB.
[0031] The adhesive is prepared by the following method: all raw materials except silane-terminated polyester polyol are added to a mixer at once, heated to 80-120°C, stirred for 1-2 hours until the materials are mixed evenly, the reaction temperature is maintained, and the mixture is stirred and dried under vacuum; the temperature is lowered to 30-50°C, silane-terminated polyester polyol is added, stirring is continued for 2-4 hours, nitrogen is introduced, and the mixture is packaged to obtain the adhesive product.
[0032] The beneficial effects of this invention are as follows:
[0033] The main innovations of this invention, which uses epoxy silane as a modified raw material to obtain silane-terminated polyester polyols, are as follows: ① Using epoxy silane containing tribromophenyl as a raw material to synthesize silane-terminated polyester polyols, the electron-withdrawing effect of halogens makes the silane groups more active, resulting in higher reactivity of the product; ② In addition, the presence of tribromophenyl increases the reactivity of the epoxy groups, effectively improving production efficiency; ③ When applied to the adhesive field, this silane-terminated polyester polyol can give adhesives higher surface properties and better strength. Detailed Implementation
[0034] The present invention will be further illustrated below with specific embodiments. These embodiments are merely illustrative and do not limit the scope of the invention.
[0035] Except for tribromophenylepoxysilanes, which are derived from Aladdin reagents, all other reactants involved in this invention are purchased from commercially available pure products.
[0036] The testing method involved in this invention:
[0037] Acid value: The acid value of polyester polyol products shall be in accordance with GBT 12008.5-20010.
[0038] The tensile strength of the adhesive refers to GB7124-1986. The preparation method of the adhesive is as follows: all raw materials except silane-terminated polyester polyol are added to a mixer at one time, heated to 80-120℃, stirred for 1 hour until the materials are uniformly mixed, the reaction temperature is maintained, and the mixture is stirred and dried under vacuum; the temperature is lowered to 30-50℃, the silane-terminated polyester polyol in the example or comparative example is added, stirring is continued for 3 hours, nitrogen is introduced and then the product is packaged to obtain the adhesive product.
[0039] The raw materials for adhesive preparation include the following components in parts by weight:
[0040]
[0041] Example 1
[0042] In a 5L stainless steel reactor equipped with a stirrer, heater, condenser, and distillation column, under nitrogen protection, 1.53 kg of triethylene glycol and 1.89 kg of adipic acid were added sequentially, along with 50 ppm of isopropyl titanate as a catalyst. The reaction was initiated, heated to 200°C at atmospheric pressure, and held at that temperature for 8 hours. Then, 0.67 kg of 2-(3,4-epoxytribromophenyl)ethyltrimethoxysilane was added, and the reaction continued for another 6 hours. After the acid value was deemed acceptable, the mixture was cooled and discharged to obtain a silane-terminated polyester polyol.
[0043] Product NMR C10 13 The main peak values (taking Example 1 as an example) are: 22.6, 24.4, 33.2, 33.6, 56.2, 61.3, 66.9, 69.3, 70, 115.1, 122, 122.9, 137, 172.3, 173.1.
[0044] The ring-opening reaction cycle was 6 hours, the tested acid value was 2.3 mg KOH / g, and the adhesive tensile strength was 1.23 MPa.
[0045] Example 2
[0046] In a 5L stainless steel reactor equipped with a stirrer, heater, condenser, and distillation column, under nitrogen protection, 1.66 kg of triethylene glycol and 1.78 kg of adipic acid were added sequentially, along with 100 ppm of isopropyl titanate as a catalyst. The reaction was initiated, heated to 200°C at atmospheric pressure, and held at that temperature for 6 hours. Then, 0.73 kg of 2-(3,4-epoxytribromophenyl)ethyltrimethoxysilane was added, and the reaction continued for another 5 hours. After the acid value was deemed acceptable, the mixture was cooled and discharged to obtain a silane-terminated polyester polyol.
[0047] The ring-opening reaction cycle was 5 hours, the tested acid value was 2.2 mg KOH / g, and the adhesive tensile strength was 0.96 MPa.
[0048] Example 3
[0049] In a 5L stainless steel reactor equipped with a stirrer, heater, condenser, and distillation column, under nitrogen protection, 1.77 kg of triethylene glycol and 1.82 kg of adipic acid were added sequentially, along with 100 ppm of tetrabutyl titanate as a catalyst. The reaction was initiated, and the temperature was raised to 180°C under normal pressure and maintained for 7 hours. Then, 0.65 kg of 2-(3,4-epoxytribromophenyl)ethyltrimethoxysilane was added, and the reaction continued for another 7 hours. After the acid value was found to be acceptable, the mixture was cooled and discharged to obtain silane-terminated polyester polyol.
[0050] The ring-opening reaction cycle was 7 hours, the tested acid value was 2.1 mg KOH / g, and the adhesive tensile strength was 0.92 MPa.
[0051] Example 4
[0052] In a 5L stainless steel reactor equipped with a stirrer, heater, condenser, and distillation column, under nitrogen protection, 1.90 kg of diethylene glycol and 1.97 kg of adipic acid were added sequentially, along with tetrabutyl titanate as a catalyst at 90 ppm of the total mass of the aforementioned raw materials. The reaction was initiated, and the temperature was raised to 160°C under normal pressure and maintained for 8 hours. Then, 0.73 kg of 3-glycidyl ether (2-tribromophenyl)propyltrimethoxysilane was added, and the reaction continued for another 6 hours. After the acid value was found to be acceptable, the mixture was cooled and discharged to obtain silane-terminated polyester polyol.
[0053] The ring-opening reaction cycle was 6 hours, the tested acid value was 2.7 mg KOH / g, and the adhesive tensile strength was 0.85 MPa.
[0054] Example 5
[0055] In a 5L stainless steel reactor equipped with a stirrer, heater, condenser, and distillation column, under nitrogen protection, 1.90 kg of diethylene glycol and 1.97 kg of adipic acid were added sequentially, along with 80 ppm of isopropyl titanate as a catalyst. The reaction was initiated, heated to 190°C at atmospheric pressure, and held at that temperature for 7 hours. Then, 0.69 kg of 3-glycidyl ether (2-tribromophenyl)propyltriethoxysilane was added, and the reaction continued for another 6 hours. After the acid value was found to be acceptable, the mixture was cooled and discharged to obtain a silane-terminated polyester polyol.
[0056] The ring-opening reaction cycle was 6 hours, the tested acid value was 2.2 mg KOH / g, and the adhesive tensile strength was 1.05 MPa.
[0057] Example 6
[0058] In a 5L stainless steel reactor equipped with a stirrer, heater, condenser, and distillation column, under nitrogen protection, 1.81 kg of diethylene glycol and 1.93 kg of adipic acid were added sequentially, along with 80 ppm of isopropyl titanate as a catalyst. The reaction was initiated, heated to 190°C at atmospheric pressure, and held at that temperature for 7 hours. Then, 0.69 kg of 2-(3,4-epoxytribromophenyl)ethyltrimethoxysilane was added, and the reaction continued for another 6 hours. After the acid value was deemed acceptable, the mixture was cooled and discharged to obtain a silane-terminated polyester polyol.
[0059] The ring-opening reaction cycle was 6 hours, the tested acid value was 2.2 mg KOH / g, and the adhesive tensile strength was 1.05 MPa.
[0060] Example 7
[0061] In a 5L stainless steel reactor equipped with a stirrer, heater, condenser, and distillation column, under nitrogen protection, 1.75 kg of triethylene glycol and 1.83 kg of adipic acid were added sequentially, along with 80 ppm of isopropyl titanate as a catalyst. The reaction was initiated, heated to 200°C at atmospheric pressure, and held at that temperature for 6 hours. Then, 0.79 kg of 2-(3,4-epoxytribromophenyl)ethyltriethoxysilane was added, and the reaction continued for another 7 hours. After the acid value was deemed acceptable, the mixture was cooled and discharged to obtain silane-terminated polyester polyol.
[0062] The ring-opening reaction cycle was 7 hours, the tested acid value was 2.1 mg KOH / g, and the adhesive tensile strength was 1.08 MPa.
[0063] Comparative Example 1
[0064] In a 5L stainless steel reactor equipped with a stirrer, heater, condenser, and distillation column, under nitrogen protection, 1.75 kg of triethylene glycol and 1.83 kg of adipic acid were added sequentially, along with 80 ppm of isopropyl titanate as a catalyst. The reaction was initiated, heated to 200°C at atmospheric pressure, and held at that temperature for 6 hours. Then, 0.79 kg of (3-isocyanopropyl)trimethoxysilane was added, and the reaction continued for 13 hours. After the acid value was found to be acceptable, the mixture was cooled and discharged to obtain silane-terminated polyester polyol.
[0065] The ring-opening reaction cycle was 13 hours, the tested acid value was 4.1 mg KOH / g, and the adhesive tensile strength was 0.71 MPa.
[0066] Comparative Example 2
[0067] In a 5L stainless steel reactor equipped with a stirrer, heater, condenser, and distillation column, under nitrogen protection, 1.75 kg of triethylene glycol and 1.83 kg of adipic acid were added sequentially, along with 80 ppm of isopropyl titanate as a catalyst. The reaction was initiated, heated to 200°C at atmospheric pressure, and held at that temperature for 6 hours. Then, 0.1 kg of 2-(3,4-epoxytribromophenyl)ethyltriethoxysilane was added, and the reaction continued for another 7 hours. After the acid value was deemed acceptable, the mixture was cooled and discharged to obtain silane-terminated polyester polyol.
[0068] The ring-opening reaction cycle was 13 hours, the tested acid value was 2.0 mg KOH / g, and the adhesive tensile strength was 0.72 MPa.
[0069] The above description is only a preferred embodiment of the present invention. It should be noted that those skilled in the art can make several improvements and additions without departing from the method of the present invention, and these improvements and additions should also be considered within the scope of protection of the present invention.
Claims
1. A silane-terminated polyester polyol, characterized in that, The silane-terminated polyester polyol is obtained by polycondensation reaction of tribromophenylepoxysilane, small molecule diol and small molecule diacid as raw materials in the presence of a catalyst. Based on the total mass of raw materials being 100%, the percentage of each substance used is as follows: Small molecule dicarboxylic acids: 33-65%; Small molecule diols 30-60%; Tribromophenylepoxysilane 5-30%.
2. The silane-terminated polyester polyol as described in claim 1, characterized in that, Based on the total mass of raw materials being 100%, the percentage of each substance used is as follows: Small molecule dicarboxylic acids 35-50%; Small molecule diols 35-55%; 10-25% tribromophenylepoxysilane.
3. The silane-terminated polyester polyol as described in claim 1, characterized in that, The catalyst is selected from one or more of tetrabutyl titanate, isopropyl titanate, stannous octoate, triethylamine octoate, tripropylamine, and p-toluenesulfonic acid; and / or the amount of catalyst used is 50-200 ppm of the total mass of the raw materials.
4. The silane-terminated polyester polyol as described in claim 3, characterized in that, The amount of catalyst used is 50-100 ppm of the total mass of the raw materials.
5. The silane-terminated polyester polyol according to any one of claims 1-4, characterized in that, The tribromophenyl epoxysilane is selected from one or more of 2-(3,4-epoxytribromophenyl)ethyltriethoxysilane, 2-(3,4-epoxytribromophenyl)ethyltrimethoxysilane, 3-glycidyl ether(2-tribromophenyl)propyltrimethoxysilane, and 3-glycidyl ether(2-tribromophenyl)propyltriethoxysilane.
6. The silane-terminated polyester polyol according to any one of claims 1-4, characterized in that, The small molecule diol is selected from diols having 2-8 carbon atoms; and / or, the small molecule dicarboxylic acid is selected from dicarboxylic acids having 4-10 carbon atoms.
7. The silane-terminated polyester polyol according to any one of claims 1-4, characterized in that, The small molecule diol is selected from one or more of ethylene glycol, 1,3-propanediol, 1,4-butanediol, 1,5-pentanediol, diethylene glycol, triethylene glycol, 1,2-propanediol, dipropylene glycol, 2-methyl-2,4-pentanediol, and 3-methyl-1,5-pentanediol; the small molecule dicarboxylic acid is selected from one or two of succinic acid, adipic acid, pimelic acid, azelaic acid, terephthalic acid, and isophthalic acid.
8. The method for preparing silane-terminated polyester polyols according to any one of claims 1-7, characterized in that, The method includes: in an inert atmosphere, first adding a small molecule dicarboxylic acid and a small molecule diol to carry out the first step of esterification reaction; when the acid value decreases to 10-60 mgKOH / g, adding tribromophenylepoxysilane; and stopping the reaction when the acid value decreases to 3 mgKOH / g.
9. The preparation method according to claim 8, characterized in that, The first step of the esterification reaction is carried out at a temperature of 150-250℃; and / or the first step of the esterification reaction is carried out for a time of 5-15 h; and / or the second step of the reaction is carried out after the addition of tribromophenylepoxysilane for a time of 5-10 h.
10. The preparation method according to claim 9, characterized in that, The first step of the esterification reaction is carried out at a temperature of 160-200℃; and / or the first step of the esterification reaction is carried out for a time of 6-8 hours; and / or, after the addition of tribromophenylepoxysilane in the second step, the reaction time is 6-9 hours.
11. An adhesive, characterized in that, The adhesive comprises the following components in parts by weight: 100 parts of silane-terminated modified polyester polyol; Filler: 80-120 parts; Dehydrating agent: 2-5 parts; Catalyst: 1-3 parts; Plasticizer: 100-150 parts; Whitening agent: 10-20 parts; The silane-terminated modified polyester polyol is selected from the silane-terminated polyester polyol as described in any one of claims 1-7 or the silane-terminated polyester polyol prepared by the preparation method as described in any one of claims 8-10.
12. The adhesive as claimed in claim 11, characterized in that: The filler is selected from one or more of titanium dioxide, calcium carbonate, clay, and quartz powder; and / or the catalyst is selected from one or more of organotin, tertiary amines, and organobismuth; and / or the plasticizer is selected from one or more of dioctyl phthalate, dioctyl sebacate, and dibutyl phthalate.
13. The method for preparing the adhesive as described in claim 11 or 12, characterized in that, The process includes the following steps: Add all raw materials except silane-terminated polyester polyol to a mixer at once, heat to 80-120℃, stir for 1-2 hours until the materials are evenly mixed, maintain the reaction temperature, and stir and dry under vacuum; cool to 30-50℃, add silane-terminated polyester polyol, continue stirring for 2-4 hours, fill with nitrogen, and then package to obtain the adhesive product.