Silane-modified double-bond functionalized polyether resin as well as preparation method and application thereof

Abstract

The invention discloses silane modified double-bond functionalized polyether resin which is prepared from the following components in parts by weight: 90-97 parts by weight of double-bond functionalized polyether polyol; 2.9 to 5.6 parts by weight of isocyanate group silane; 1.9 to 3.7 parts by weight of hydrogen-containing silane; 0.03 to 0.06 part by weight of a hydrosilylation catalyst; and 0.02-0.1 part by weight of an organic bismuth catalyst. In the preparation process of the silane modified double-bond functionalized polyether resin, the process is simple, pollution is little, odor is low, storage is stable, and MS glue prepared from the resin is good in extrudability, excellent in elastic recovery rate, high in hardness and elastic modulus and good in tensile strength.

Description

Technical Field

[0001] The invention belongs to the technical field of MS glue, and specifically relates to a silane-modified double-bond functionalized polyether resin and a preparation method and application thereof. Background Art

[0002] Silane-terminated polyether sealant (MS sealant) is a new generation of sealant developed after polysulfide sealant, silicone sealant, and polyurethane sealant. It has good mechanical strength, extrusion resistance, and stain resistance. The product does not contain volatile solvents and is one of the mainstream development directions of new elastic sealants at home and abroad. MS sealant is based on silane-terminated polyether resin. The resin has a long-chain polyether as the main chain and a hydrolyzable alkoxysilane group as the end cap. After curing, it can form a network structure with Si-O-Si as the cross-linking point and flexible polyether long chains connected, giving the sealant good weather resistance, water resistance, and aging resistance. In addition, due to the low surface energy of silane-terminated polyether resin, it has good wettability to metals, plastics, and glass, thus producing excellent bonding properties to the substrate.

[0003] There are three main methods known for preparing silane-terminated polyether resins: (1) Polyether polyols are first reacted with twice the amount of diisocyanate to prepare isocyanate-terminated polyether resins, and then reacted with active hydrogen-containing silanes to obtain silane-terminated polyether resins. Although the resin obtained by this method has a higher viscosity, there is a risk of gelation during the preparation process and the operability is poor. (2) Polyether polyols are directly reacted with isocyanate-containing silanes to obtain silane-terminated polyether resins. However, the degree of crosslinking after curing of the resin obtained by this method is low and the strength is not ideal. (3) Polyether polyols are first reacted with allyl chloride to obtain allyl-terminated polyethers, and then reacted with hydrogen-containing silanes for hydrosilylation to obtain silane-terminated polyether resins. The disadvantages of this method are that the reaction process is cumbersome and allyl chloride, which is highly toxic and irritating, is used to introduce double bonds into the polyether.

[0004] In order to solve the above problems, it is urgent to develop a MS glue that has simple process, environmental protection, good operability and high strength after curing. Summary of the invention

[0005] The purpose of the present invention is to provide a silane-modified double-bond functionalized polyether resin, which has high strength after curing, and has a simple preparation method, is environmentally friendly and has good operability.

[0006] Another object of the present invention is to provide a method for preparing the silane-modified double-bond functionalized polyether resin, which is simple, environmentally friendly and has good operability.

[0007] Another object of the present invention is to provide the application of the silane-modified double-bond functionalized polyether resin as MS glue, which has high strength after curing.

[0008] The purpose of this application is achieved by the following technical solutions:

[0009] A silane-modified double-bond functionalized polyether resin is prepared from the following components in parts by weight:

[0010] 90 to 97 parts by weight of double-bond functionalized polyether polyol,

[0011] 2.9 to 5.6 parts by weight of isocyanate silane,

[0012] 1.9 to 3.7 parts by weight of hydrogen-containing silane,

[0013] 0.03 to 0.06 parts by weight of hydrosilylation catalyst,

[0014] 0.02-0.1 parts by weight of organic bismuth catalyst

[0015] Compared with ordinary polyether polyols, double-bond functionalized polyether polyols have additional allyl groups grafted onto their main chains while retaining the hydroxyl groups of polyether polyols. The hydroxyl and allyl groups can react with isocyanate silanes and hydrogen-containing silanes, increasing the content of hydrolyzable silanes on the silane-modified polyether resin, giving it a higher crosslinking density and better mechanical properties when cured.

[0016] In addition, the process of preparing the silane-modified double-bond functionalized polyether resin using the above raw materials does not involve solvents and irritating compounds, and is environmentally friendly and pollution-free or less polluting.

[0017] Preferably, the isocyanate silane is selected from at least one of isocyanate propyl triethoxy silane, 3-isocyanate propyl trimethoxy silane, 3-isocyanate propyl methyl diethoxy silane and methyl-(3-isocyanate propyl) dimethoxy silane.

[0018] Preferably, the hydrogen-containing silane is selected from at least one of trimethoxysilane and triethoxysilane.

[0019] Preferably, the hydrosilylation catalyst is selected from at least one of chloroplatinic acid, 1,3-divinyl-1,1,3,3-tetramethyldisiloxane platinum, palladium chloride, tetrakis(triphenylphosphine)palladium, octacarbonyl dicobalt, tetracarbonyl nickel, and hexacarbonyl chromium.

[0020] Preferably, the organic bismuth catalyst is bismuth neododecanoate.

[0021] By using the above-mentioned isocyanate silane, hydrogen-containing silane and hydrosilylation catalyst, the hydroxyl and allyl groups on the double-bond functionalized polyether polyol can be reacted with the isocyanate silane and hydrogen-containing silane through a simple "one-pot reaction", and the process is simple.

[0022] Preferably, the double bond functionalized polyether polyol is prepared by reacting the following components in parts by weight:

[0023] Allyl glycidyl ether 1.73-2.85 parts by weight,

[0024] 2.70 to 4.20 parts by weight of initiator,

[0025] 93 to 96 parts by weight of propylene oxide,

[0026] The ring-opening catalyst is 0.002 to 0.01 parts by weight.

[0027] Ordinary polyether polyols only have reactive hydroxyl groups at the left and right end caps. When preparing silane-modified polyether resins, only hydroxyl groups can be used for reaction. Therefore, the obtained silane-modified polyether resins often have low crosslinking density and low strength. In this regard, the present invention adopts the above technical scheme, introduces allyl glycidyl ether as an epoxy monomer, and participates in the ring-opening reaction in the preparation process of polyether polyols together with propylene oxide, and directly synthesizes double-bond functionalized polyether polyols with allyl groups in the main chain. The hydroxyl and allyl groups on the double-bond functionalized polyether polyols can react with isocyanate silanes and hydrogen-containing silanes, greatly improving the crosslinking density and strength of the silane-modified polyether resin.

[0028] Preferably, the initiator is propylene glycol polyoxypropylene ether, with a number average molecular weight of 400, purchased from Jiangsu Zhongshan New Materials Co., Ltd.

[0029] Preferably, the ring-opening catalyst is selected from a double metal cyanide complex catalyst (DMC). The use of the above catalyst has higher catalytic efficiency, faster reaction speed, and no post-treatment refining step of the polyether is required.

[0030] The double-bond functionalized polyether polyol prepared by the above technical scheme has an unsaturation value of 0.16-0.26 mmol / g, an acid value of no more than 0.08 mgKOH / g, a molecular weight of 8000-12000, and a hydroxyl value of 9-14 mgKOH / g.

[0031] The present invention also provides a preparation method of the silane-modified double-bond functionalized polyether resin, comprising the following steps: reacting a mixture of a double-bond functionalized polyether polyol, a hydrogen-containing silane, a hydrosilylation catalyst, an organic bismuth catalyst, and an isocyanate silane in an inert atmosphere at 20-40° C. for 20-30 hours, and then reacting at 70-85° C. for 4-6 hours to obtain the silane-modified double-bond functionalized polyether resin.

[0032] Preferably, the dosage of each component in the mixture is as follows:

[0033] 90 to 97 parts by weight of double-bond functionalized polyether polyol,

[0034] 2.9 to 5.6 parts by weight of isocyanate silane,

[0035] 1.9 to 3.7 parts by weight of hydrogen-containing silane,

[0036] 0.03 to 0.06 parts by weight of hydrosilylation catalyst,

[0037] 0.02-0.1 parts by weight of organic bismuth catalyst

[0038] By adopting the above technical scheme, the preparation process is simple, no solvent is needed, and the environment is environmentally friendly with no pollution or little pollution. The prepared silane-modified double-bond functionalized polyether resin can be used to prepare MS glue.

[0039] Preferably, the double bond functionalized polyether polyol is prepared by the following method:

[0040] Put the initiator and the ring-opening catalyst into the reaction kettle, start stirring, and after nitrogen replacement, evacuate at 140-160°C for 1h, and turn off the vacuum; first introduce propylene oxide, and then gradually introduce the mixture of allyl glycidyl ether and propylene oxide into the kettle. During the feeding process, the temperature is maintained at 140-150°C and the pressure is ≤0.1MPa; after the feeding is completed, continue stirring at 140-160°C, then evacuate, cool down and discharge.

[0041] In the preferred technical solution, the mass ratio of allyl glycidyl ether to propylene oxide in the mixture of allyl glycidyl ether and propylene oxide is 1:0.9-1.1.

[0042] The double-bond functionalized polyether polyol prepared by the method retains the hydroxyl group and has an additional allyl group grafted onto the main chain, thereby avoiding the use of allyl chloride which is highly irritating and polluting.

[0043] The present invention also provides a MS glue, which is prepared from the following components in parts by weight:

[0044] 30 to 40 parts by weight of silane-modified double-bond functionalized polyether resin,

[0045] Heavy calcium carbonate powder 60-70 parts by weight,

[0046] Silane coupling agent 0.5-1.5 parts by weight.

[0047] By adopting the above technical solution, the prepared MS glue has a larger elongation at break, higher tensile strength and hardness.

[0048] Preferably, the heavy calcium carbonate powder is selected from at least one of 400 mesh, 600 mesh, 800 mesh, 1000 mesh, 1200 mesh and 2000 mesh.

[0049] Preferably, the silane coupling agent is selected from one of vinyltrimethoxysilane, γ-aminopropyltriethoxysilane, γ-glycidyloxypropyltrimethoxysilane, γ-methacryloxypropyltrimethoxysilane, γ-mercaptopropyltriethoxysilane and γ-mercaptopropyltrimethoxysilane.

[0050] Preferably, the MS glue is prepared by the following method: silane-modified double-bond functionalized polyether resin, heavy calcium carbonate powder and silane coupling agent are mixed by a homogenizer to obtain MS glue.

[0051] Beneficial effects of the present invention: The silane-modified double-bond functionalized polyether resin of the present invention is first polymerized from allyl glycidyl ether, an initiator, propylene oxide, and a ring-opening catalyst to form a double-bond functionalized polyether polyol, and then the double-bond functionalized polyether polyol reacts with isocyanate silane and hydrogen-containing silane to obtain a silane-modified double-bond functionalized polyether resin. The present invention introduces an allyl-containing epoxy monomer to directly graft allyl groups on the polyether main chain, thereby avoiding the use of chlorinated allyl with greater irritation; isocyanate silane and hydrogen-containing silane are used to react with the double-bond functionalized polyether polyol, thereby effectively improving the crosslinking density of the MS glue after curing, so that it has higher bonding performance and tensile strength. The preparation method of the silane-modified double-bond functionalized polyether resin of the present invention is simple, has good operability, does not use solvents, does not generate waste liquid, is environmentally friendly and has no pollution or less pollution. The MS glue prepared using the silane-modified double-bond functionalized polyether resin has good extrudability, excellent elastic recovery rate, high hardness, and good tensile strength at break. DETAILED DESCRIPTION

[0052] The present application is described in detail below in conjunction with embodiments, but the present application is not limited to these embodiments.

[0053] Unless otherwise specified, the raw materials in the examples of this application were purchased through commercial channels.

[0054] Unless otherwise specified, conventional methods and instruments were used for testing.

[0055] Preparation Example 1

[0056] 100g N-204 (propylene glycol polyoxypropylene ether, number average molecular weight of 400, purchased from Jiangsu Zhongshan New Materials Co., Ltd.) and 0.05g double metal cyanide complex catalyst (DMC, cobalt / zinc double metal cyanide complex catalyst, purchased from Huai'an Bader Polyurethane Co., Ltd.) were added to the reaction kettle, stirring was turned on, and after nitrogen replacement 3 times, vacuum was evacuated at 150°C for 1h, and the vacuum was turned off; 2169g propylene oxide was gradually introduced first, and then a mixture of allyl glycidyl ether and propylene oxide in an equal mass ratio, totaling 131g, was gradually introduced into the kettle. During the entire feeding process, the temperature was maintained at 145±5°C and the pressure was ≤0.1MPa; after the feeding was completed, stirring was continued at 150°C for 1h, and then vacuum was evacuated at 155°C for 1h, and the temperature was lowered and the material was discharged to obtain a double bond functionalized polyether polyol A with a number average molecular weight of 8000.

[0057] Preparation Example 2

[0058] 100g N-204 (propylene glycol polyoxypropylene ether, number average molecular weight of 400, purchased from Jiangsu Zhongshan New Materials Co., Ltd.) and 0.08g double metal cyanide complex catalyst (DMC, cobalt / zinc double metal cyanide complex catalyst, purchased from Huai'an Bader Polyurethane Co., Ltd.) were added to the reaction kettle, stirring was turned on, and after nitrogen replacement 3 times, vacuum was evacuated at 150°C for 1h, and the vacuum was turned off; 3369g propylene oxide was gradually introduced first, and then a mixture of allyl glycidyl ether and propylene oxide in an equal mass ratio, totaling 131g, was gradually introduced into the kettle. During the entire feeding process, the temperature was maintained at 145±5°C and the pressure was ≤0.1MPa; after the feeding was completed, stirring was continued at 150°C for 1h, and then vacuum was evacuated at 155°C for 1h, and the temperature was lowered and the material was discharged to obtain a double bond functionalized polyether polyol B with a number average molecular weight of 12000.

[0059] Comparative Example 1

[0060] ZSN-280: propylene glycol polyoxypropylene ether, purchased from Jiangsu Zhongshan New Materials Co., Ltd., number average molecular weight 8000.

[0061] Comparative Example 2

[0062] ZSN-2120: Propylene glycol polyoxypropylene ether, purchased from Jiangsu Zhongshan New Materials Co., Ltd., with a number average molecular weight of 12,000.

[0063] Table 1 Test results of Preparation Examples 1-2 and Comparative Examples 1-2

[0064]

[0065] Example 1

[0066] Under nitrogen protection, 100 g of the double bond functionalized polyether polyol A obtained in Preparation Example 1, 2.99 g of trimethoxysilane, 0.05 g of chloroplatinic acid, 5.03 g of 3-isocyanatepropyltrimethoxysilane and 0.05 g of bismuth neododecanoate were added to the reactor, stirred and heated to 30°C and reacted at 30°C for 24 hours, continued to stir and heat to 80°C and reacted at 80°C for 4 hours, cooled and discharged to obtain silane-modified double bond functionalized polyether resin A.

[0067] Example 2

[0068] Under nitrogen protection, 100 g of the double bond functionalized polyether polyol B obtained in Preparation Example 2, 2.02 g of trimethoxysilane, 0.05 g of chloroplatinic acid, 3.40 g of 3-isocyanatepropyltrimethoxysilane and 0.05 g of bismuth neododecanoate were added to the reactor, stirred and heated to 30°C and reacted at 30°C for 24 hours, continued to stir and heat to 80°C and reacted at 80°C for 4 hours, cooled and discharged to obtain silane-modified double bond functionalized polyether resin B.

[0069] Example 3

[0070] Under nitrogen protection, 100 g ZSN-280, 5.07 g 3-isocyanatepropyltrimethoxysilane and 0.05 g bismuth neododecanoate were added to a reaction kettle, stirred and heated to 80° C. and reacted at 80° C. for 4 h, cooled and discharged to obtain silane-modified double-bond functionalized polyether resin C.

[0071] Example 4

[0072] Under nitrogen protection, 100 g ZSN-2120, 3.36 g 3-isocyanatepropyltrimethoxysilane and 0.05 g bismuth neododecanoate were added to a reaction kettle, stirred and heated to 80° C. and reacted at 80° C. for 4 h, cooled and discharged to obtain silane-modified double-bond functionalized polyether resin D.

[0073] Application Example 1

[0074] 100 g of silane-modified double-bond functionalized polyether resin A (prepared in Example 1), 200 g of 1200 mesh heavy calcium carbonate powder and 3 g of γ-glycidyloxypropyltrimethoxysilane were added into a homogenizer, and the mixing speed of the homogenizer was set to 1000 r / min for 15 min to obtain MS glue.

[0075] The preparation process of Application Examples 2-4 is the same as that of Application Example 1, except that the raw materials are different from those of Application Example 1 (as shown in Table 3). Specifically, the silane-modified double-bond functionalized polyether resin B, silane-modified polyether resin C, and silane-modified polyether resin D obtained in Examples 2-4 are used to replace the silane-modified double-bond functionalized polyether resin A in Application Example 1 to prepare the corresponding MS glue, and the rest remains unchanged.

[0076] Table 3 Raw materials and feed amounts in application examples 1-4

[0077]

[0078] The MS glues prepared in Application Examples 1-4 were subjected to performance tests according to standard GB / T14683-2017, and the test results are shown in Table 4.

[0079] Table 4 Performance test results of MS glue prepared in application examples 1-4

[0080] Test items Application Example 1 Application Example 2 Application Example 3 Application Example 4 <![CDATA[Density (g / cm 3 )]]> 1.52 1.51 1.52 1.50 Sag (mm) 0 0 0 0 Extrusion capacity (mL / min) 285 261 288 266 Surface drying time (h) 1.2 1.3 1.8 1.9 Elastic recovery rate (%) 65 64 65 65 Tensile modulus (23℃, MPa) 0.65 0.72 0.30 0.36 Hardness (Shore A) 55 65 25 36 Tensile strength at break (MPa) 2.8 3.1 1.3 1.5 Elongation at break (%) 380 336 671 625

[0081] It can be seen from Table 4 that the MS glue prepared by the present invention has good extrusion performance, excellent elastic recovery rate, high hardness and good tensile strength at break.

[0082] Comparison between Application Example 1 and Application Example 3, and between Application Example 2 and Application Example 4, shows that the MS prepared based on the silane-modified double-bond functionalized polyether resin of the present invention has a shorter surface drying time, higher tensile modulus, hardness and tensile strength at break. The main reason is that in addition to the siloxane groups on both sides of the molecular chain of the silane-modified double-bond functionalized polyether resin, siloxane is additionally grafted on the main chain, so that it has higher crosslinking density, tensile modulus, hardness and tensile strength at break when cured.

[0083] The above are only a few embodiments of the present application and do not constitute any form of limitation to the present application. Although the present application is disclosed as above with preferred embodiments, it is not intended to limit the present application. Any technician familiar with the profession, without departing from the scope of the technical solution of the present application, using the technical content disclosed above to make slight changes or modifications are equivalent to equivalent implementation cases and fall within the scope of the technical solution.

Claims

1. A silane-modified double-bond functionalized polyether resin, characterized in that: It is prepared from the following components in parts by weight: 90 to 97 parts by weight of double-bond functionalized polyether polyol, 2.9 to 5.6 parts by weight of isocyanate silane, 1.9-3.7 parts by weight of hydrogen-containing silane, 0.03 to 0.06 parts by weight of hydrosilylation catalyst, 0.02-0.1 parts by weight of organic bismuth catalyst 2. The silane-modified double-bond functionalized polyether resin according to claim 1, characterized in that: The double bond functionalized polyether polyol is prepared by reacting the following components in parts by weight: Allyl glycidyl ether 1.73-2.85 parts by weight, 2.70 to 4.20 parts by weight of initiator, 93 to 96 parts by weight of propylene oxide, The ring-opening catalyst is 0.002 to 0.01 parts by weight.

3. The silane-modified double-bond functionalized polyether resin according to claim 2, characterized in that The isocyanate silane is selected from at least one of isocyanate propyl triethoxysilane, 3-isocyanate propyl trimethoxysilane, 3-isocyanate propyl methyl diethoxysilane, and methyl-(3-isocyanate propyl) dimethoxysilane; the hydrogen-containing silane is selected from at least one of trimethoxysilane and triethoxysilane; the hydrosilylation catalyst is selected from at least one of chloroplatinic acid, 1,3-divinyl-1,1,3,3-tetramethyldisiloxane platinum, palladium chloride, tetrakis(triphenylphosphine)palladium, octacarbonyl dicobalt, tetracarbonyl nickel, and hexacarbonyl chromium; the organic bismuth catalyst is bismuth neododecanoate.

4. The silane-modified double-bond functionalized polyether resin according to claim 3, characterized in that: The initiator is propylene glycol polyoxypropylene ether, produced by Jiangsu Zhongshan New Materials Co., Ltd., with a number average molecular weight of 400; the ring-opening catalyst is a double metal cyanide complex catalyst.

5. The method for preparing the silane-modified double-bond functionalized polyether resin according to any one of claims 1 to 4, characterized in that: The method comprises the following steps: reacting a mixture of double-bond functionalized polyether polyol, hydrogen-containing silane, a hydrosilylation catalyst, an organic bismuth catalyst and an isocyanate silane in an inactive atmosphere at 20-40° C. for 20-30 hours, and then reacting at 70-85° C. for 4-6 hours to obtain the silane-modified double-bond functionalized polyether resin.

6. The preparation method according to claim 5, characterized in that The double-bond functionalized polyether polyol comprises 90 to 97 parts by weight, isocyanate silane 2.9 to 5.6 parts by weight, hydrogen-containing silane 1.9 to 3.7 parts by weight, hydrosilylation catalyst 0.03 to 0.06 parts by weight, and organic bismuth catalyst 0.02-0.1 parts by weight.

7. The preparation method according to claim 6, characterized in that: The double-bond functionalized polyether polyol is prepared by the following method: putting an initiator and a ring-opening catalyst into a reaction kettle, starting stirring, purging with nitrogen, evacuating at 140°C-160°C, and closing the vacuum; firstly introducing propylene oxide, and then introducing a mixture of allyl glycidyl ether and propylene oxide into the kettle, during which the temperature is maintained at 140-150°C and the pressure is ≤0.1MPa; after the feeding is completed, continuing stirring at 140°C-160°C, then evacuating, cooling and discharging.

8. The preparation method according to claim 7, characterized in that The mass ratio of allyl glycidyl ether to propylene oxide in the mixture of allyl glycidyl ether and propylene oxide is 1:0.9-1.

1.

9. A MS glue, characterized in that: The MS glue is prepared from the following components in parts by weight: 30-40 parts by weight of silane-modified double-bond functionalized polyether resin, 60-70 parts by weight of heavy calcium carbonate powder, and 0.5-1.5 parts by weight of silane coupling agent; The silane-modified double-bond functionalized polyether resin is selected from the silane-modified double-bond functionalized polyether resin described in any one of claims 1 to 4, and the silane-modified double-bond functionalized polyether resin prepared by the preparation method described in any one of claims 5 to 8; the silane coupling agent is selected from vinyltrimethoxysilane, γ-aminopropyltriethoxysilane, γ-glycidyloxypropyltrimethoxysilane, γ-methacryloxypropyltrimethoxysilane, γ-mercaptopropyltriethoxysilane, and γ-mercaptopropyltrimethoxysilane; the heavy calcium carbonate powder is selected from at least one of 400 mesh, 600 mesh, 800 mesh, 1000 mesh, 1200 mesh, and 2000 mesh.

10. The MS glue according to claim 9, characterized in that: The silane-modified double-bond functionalized polyether resin, heavy calcium carbonate powder and silane coupling agent are mixed by a homogenizer to obtain MS glue.

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