A process for the preparation of an isocyanatosilane-modified polyether polymer

Abstract

The application relates to the technical field of MS resin formula process, in particular to a preparation method of isocyanate silane modified polyether polymer, S1, amino silane coupling agent is slowly added into MDI50 under a temperature environment of 40-60 DEG C; S2, the isocyanate silane is obtained after 1-2h of dropwise addition and 8-16h of continuous reaction; S3, polyether polyol is dehydrated and degassed under a vacuum condition at 100-120 DEG C for 2-3h; S4, then the temperature is lowered to 70-90 DEG C, the isocyanate silane in S2 is added into the polyether polyol and stirred uniformly; S5, finally, a catalyst is added, and the isocyanate silane modified polyether polymer is obtained after 3-8h of reaction under an environment of 80-100 DEG C and then vacuum removal of air bubbles at the reaction temperature; the preparation method of the isocyanate silane modified polyether polymer has higher elongation.

Description

TECHNICAL FIELD

[0001] The present application relates to MS resin formula process technical field, especially to a kind of preparation method of isocyanate group silane modified polyether polymer. BACKGROUND

[0002] After silane modified polyether polymer is cured, it can be strongly chemically bonded with the surface of various substrates (such as glass, metal, etc.), and the silane modified polyether polymer can be used as the base polymer of silane modified sealant, adhesive or coating, and is widely used.

[0003] At present, the MS resin formula process of domestic formed commodity type is generally divided into two kinds:

[0004] One is that polyether is directly reacted with isocyanate group silane, such as 3-isocyanate propyl trimethoxysilane, gamma-isocyanate propyl triethoxysilane, methyl-(3-isocyanate propyl) dimethyl silane and 3-isocyanate propyl methyl diethoxysilane, to generate silane modified polyether polymer resin, which has the advantages of simple process, mild reaction, uniform molecular weight of produced resin and low viscosity, and the disadvantage is that the price of isocyanate group silane is high, resulting in high cost of silane modified polyether polymer;

[0005] The second kind is that polyether is first reacted with isocyanate such as MDI, TDI, IPDI and HDI, and then end-capped with silane to generate silane modified polyether polymer resin, which has the advantages of low price, and the disadvantage is that the reaction is violent, chain extension is obvious, molecular weight is not uniform, resin viscosity is large, which is not conducive to the next step of production, and elongation is low. SUMMARY

[0006] The present application aims at solving the problems existing in the prior art, and provides a preparation method of isocyanate group silane modified polyether polymer.

[0007] In order to achieve the above-mentioned purpose, the technical scheme adopted by the present application is as follows:

[0008] A preparation method of isocyanate group silane modified polyether polymer is designed, and the specific steps are as follows:

[0009] S1, slowly drop amino silane coupling agent into MDI 50 under the temperature environment of 40-60℃;

[0010] S2, drop for 1-2h, continue to react for 8-16h to obtain isocyanate group silane;

[0011] S3, dehydrate and degasify polyether polyol under vacuum condition at 100-120℃ for 2-3h;

[0012] S4, then cooling to 70-90℃, the isocyanate ester silane in S2 is added to the polyether polyol, stirring evenly;

[0013] S5, finally in the presence of a catalyst, 80-100℃ reaction for 3-8h, followed by vacuum removal of bubbles at the reaction temperature, to obtain isocyanate silane modified polyether polymer.

[0014] Preferably, the molar ratio of isocyanate of MDI50 to amino of amino silane is 1.1-1.5:2.

[0015] Preferably, MDI50 is 2.4-diphenylmethane diisocyanate.

[0016] Preferably, the functionality of the polyether polyol is 2 or 3, and the number average molecular weight is 4000-18000.

[0017] Preferably, the catalyst in S5 is dibutyltin dilaurate, stannous octoate or dibutyltin diacetate.

[0018] Preferably, the amino silane coupling agent is γ-aminopropyl trimethoxysilane, γ-aminopropyl triethoxysilane, γ-aminopropyl methyl dimethoxysilane.

[0019] Preferably, the molar ratio of isocyanate of MDI50 to amino of amino silane coupling agent is 1.1-1.5:2.

[0020] Preferably, the dehydration and degassing temperature in S3 is 100-120℃.

[0021] The preparation method of the isocyanate silane modified polyether polymer has the advantages that: the preparation method of the isocyanate silane modified polyether polymer, by reacting KH540, KH530, KH550 (preferably KH540) with the end group NCO in MDI50, generates silane with only one NCO group, which can be used for producing isocyanate silane modified polyether polymer by polyether end-capping, the produced isocyanate silane modified polyether polymer resin has higher elongation, and since MDI50 is 2.4-diphenylmethane diisocyanate, the positions of the NCO groups are different, resulting in different activities, the hydrogen group will preferentially react with the more active one of the NCO groups, leaving the other NCO group for the next end-capping reaction, the chain extension phenomenon is not obvious, the reaction is mild and controllable, the chain length is uniform, the product has low viscosity, is beneficial to production, has high elongation, and is cheap. BRIEF DESCRIPTION OF DRAWINGS

[0022] Figure 1 The flowchart of the preparation method of the isocyanate silane modified polyether polymer is shown. DETAILED DESCRIPTION

[0023] The technical solutions in the embodiments of the present application will be clearly and completely described below with reference to the drawings in the embodiments of the present application. Obviously, the described embodiments are only some of the embodiments of the present application, but not all of the embodiments of the present application.

[0024] Referring to Figure 1 A preparation method of an isocyanate-based silane modified polyether polymer, and the specific steps are as follows:

[0025] S1, slowly drop the amino silane coupling agent into MDI50 under a temperature environment of 40-60℃;

[0026] S2, after dropping for 1-2h, continue to react for 8-16h to obtain the isocyanate-based silane;

[0027] S3, dehydrate and degas the polyether polyol under a vacuum condition at 100-120℃ for 2-3h;

[0028] S4, then cool to 70-90℃, add the isocyanate-based silane in S2 into the polyether polyol, and stir uniformly;

[0029] S5, finally add a catalyst, react at 80-100℃ for 3-8h, and then remove the bubbles under the reaction temperature in a vacuum condition to obtain the isocyanate-based silane modified polyether polymer.

[0030] The molar ratio of isocyanate groups of MDI50 to amino groups of the amino silane is 1.1-1.5:2.

[0031] MDI50 is 2,4-diphenylmethane diisocyanate.

[0032] The functionality of the polyether polyol is 2 or 3, and the number average molecular weight is 4000-18000.

[0033] The catalyst in S5 is dibutyltin dilaurate, stannous octoate or dibutyltin diacetate.

[0034] The amino silane coupling agent is γ-aminopropyl trimethoxysilane, γ-aminopropyl triethoxysilane or γ-aminopropyl methyl dimethoxysilane.

[0035] The molar ratio of isocyanate groups of MDI50 to amino groups of the amino silane coupling agent is 1.1-1.5:2.

[0036] The dehydration and degasification temperature in S3 is 100-120℃.

[0037] Example 1: In a four-necked flask equipped with a stirrer, a constant pressure dropping funnel and a gas inlet tube, 12 g of γ-aminopropyltrimethoxysilane was added, and stirring was started. 2,4-Diphenylmethane diisocyanate, 33 g, was added dropwise at 40°C, and the dropping was completed in 1 hour. Then the temperature was raised to 50°C, and the reaction was carried out for 5 hours to obtain isocyanate-silane A.

[0038] The polyether polyol with a molecular weight of 8000, 528 g, was dehydrated and degassed at 110°C under vacuum for 2 hours, and then the temperature was lowered to 60°C. Isocyanate-silane A and dibutyltin dilaurate (0.05% of the mass of the polyether polyol) were added in sequence, and stirring was carried out. The reaction was carried out at 90°C for 8 hours to obtain isocyanate-silane modified polyether polymer, and the viscosity was 40,000 mPa·s.

[0039] Example 2: In a four-necked flask equipped with a stirrer, a constant pressure dropping funnel and a gas inlet tube, 10 g of γ-aminopropyltrimethoxysilane was added, and stirring was started. 2,4-Diphenylmethane diisocyanate, 35 g, was added dropwise at 40°C, and the dropping was completed in 1 hour. Then the temperature was raised to 50°C, and the reaction was carried out for 5 hours to obtain isocyanate-silane B.

[0040] The polyether polyol with a molecular weight of 8000, 528 g, was dehydrated and degassed at 110°C under vacuum for 2 hours, and then the temperature was lowered to 60°C. Isocyanate-silane B and dibutyltin dilaurate (0.05% of the mass of the polyether polyol) were added in sequence, and stirring was carried out. The reaction was carried out at 90°C for 10 hours to obtain isocyanate-silane modified polyether polymer, and the viscosity was 45,000 mPa·s.

[0041] Example 3: In a four-necked flask equipped with a stirrer, a constant pressure dropping funnel and a gas inlet tube, 8 g of γ-aminopropyltrimethoxysilane was added, and stirring was started. 2,4-Diphenylmethane diisocyanate, 17.5 g, was added dropwise at 40°C, and the dropping was completed in 1 hour. Then the temperature was raised to 50°C, and the reaction was carried out for 5 hours to obtain isocyanate-silane C.

[0042] The polyether polyol with a molecular weight of 12000, 420 g, was dehydrated and degassed at 110°C under vacuum for 2 hours, and then the temperature was lowered to 60°C. Isocyanate-silane C and dibutyltin dilaurate (0.05% of the mass of the polyether polyol) were added in sequence, and stirring was carried out. The reaction was carried out at 95°C for 10 hours to obtain isocyanate-silane modified polyether polymer, and the viscosity was 55,000 mPa·s.

[0043] Example 4: In a four-necked flask equipped with a stirrer, a constant pressure dropping funnel and a gas inlet tube, 12 g of γ-aminopropyltrimethoxysilane was added, and stirring was started. 2,4-Diphenylmethane diisocyanate, 27 g, was added dropwise at 40°C, and the dropping was completed in 1 hour. Then the temperature was raised to 60°C, and the reaction was carried out for 5 hours to obtain isocyanate-silane D.

[0044] The 432 g polyether polyol with molecular weight of 8000 was dehydrated and degassed under vacuum at 110°C for 2 h, then cooled to 60°C, and then isocyanate silane D and dibutyl tin dilaurate (0.05% of the mass of the polyether polyol) were added successively, stirred uniformly, and reacted at 95°C for 10 h to obtain an isocyanate silane modified polyether polymer with a viscosity of 30000 mPa·s.

[0045] In a four-necked flask equipped with a stirrer, a constant pressure dropping funnel and a gas inlet tube, 12 g of γ-aminopropylmethyldimethoxysilane was added, stirring was started, and 2,4- diphenylmethane diisocyanate, 36.8 g, was added dropwise at 40°C, the dropping was completed within 1 h, then the temperature was raised to 50°C, and the reaction was carried out for 5 h to obtain isocyanate silane E;

[0046] The 588 g polyether polyol with molecular weight of 8000 was dehydrated and degassed under vacuum at 110°C for 2 h, then cooled to 60°C, and then isocyanate silane E and dibutyl tin dilaurate (0.05% of the mass of the polyether polyol) were added successively, stirred uniformly, and reacted at 90°C for 10 h to obtain an isocyanate silane modified polyether polymer with a viscosity of 40000 mPa·s.

[0047] In a four-necked flask equipped with a stirrer, a constant pressure dropping funnel and a gas inlet tube, 12 g of γ-aminopropyltrimethoxysilane was added, stirring was started, and 4,4- diphenylmethane diisocyanate, 33 g, was added dropwise at 40°C, the dropping was completed within 1 h, then the temperature was raised to 50°C, and the reaction was carried out for 5 h to obtain isocyanate silane F;

[0048] The 528 g polyether polyol with molecular weight of 8000 was dehydrated and degassed under vacuum at 110°C for 2 h, then cooled to 60°C, and then isocyanate silane F and dibutyl tin dilaurate (0.05% of the mass of the polyether polyol) were added successively, stirred uniformly, and reacted at 90°C for 8 h to obtain an isocyanate silane modified polyether polymer with a viscosity of 82500 mPa·s.

[0049] In a four-necked flask equipped with a stirrer, a constant pressure dropping funnel and a gas inlet tube, 12 g of γ-aminopropyltrimethoxysilane was added, stirring was started, and 4,4- diphenylmethane diisocyanate, 33 g, was added dropwise at 40°C, the dropping was completed within 1 h, then the temperature was raised to 50°C, and the reaction was carried out for 5 h to obtain isocyanate silane F;

[0050] The synthesized terminal isocyanate group polyether prepolymer is reacted with γ-aminopropyl trimethoxysilane at a molar ratio of isocyanate to silane of 1:1 at 40°C under stirring for 3h; the reaction is ended until no isocyanate exists in the system through titration, and a silane-modified polyether polymer is obtained, with a viscosity of 95000 mPa·s.

[0051] Comparative Example Three: 500g of polyether polyol with a molecular weight of 8000 is dehydrated and degassed under vacuum at 110°C for 2h, and then cooled to 80°C. 25.6g of 3-isocyanate propyl trimethoxysilane and dibutyl tin dilaurate (0.1% of the mass of the polyether polyol) are added in sequence, stirred uniformly, and reacted at 90°C for 5h to obtain a silane-modified polyether polymer, with a viscosity of 25000 mPa·s.

[0052] Examples Six to Ten: Using each of the silane-modified polyether polymers obtained in Examples One to Five respectively, a silane-modified polyether sealant is prepared through the following steps.

[0053] Mixing production is performed using a double-planet high-speed disperser;

[0054] Nano calcium carbonate (43%), active heavy calcium (19%), secondary amino silane-modified polyether polymer (15%), dioctyl phthalate (21%), β-(aminoethyl)-γ-aminopropyl trimethoxysilane (0.3%) are put into a mixing cylinder and stirred uniformly;

[0055] Vinyl trimethoxysilane (1.5%) is added, and high-speed stirring is performed until the material is uniformly dispersed and there are no particles in the material;

[0056] The temperature is lowered to below 50°C, and the vacuum is stopped;

[0057] Dibutyl tin dilaurate (0.1%) is added, stirred uniformly, and the glue is defoamed.

[0058] Comparative Examples Four to Six: Using the silane-modified polyether polymers obtained in Comparative Examples One to Three respectively, a silane-modified polyether sealant is prepared through the following steps.

[0059] Mixing production is performed using a double-planet high-speed disperser;

[0060] Nano calcium carbonate (43%), active heavy calcium (19%), secondary amino silane-modified polyether polymer (15%), dioctyl phthalate (21%), β-(aminoethyl)-γ-aminopropyl trimethoxysilane (0.3%) are put into a mixing cylinder and stirred uniformly;

[0061] Vinyl trimethoxysilane (1.5%) is added, and high-speed stirring is performed until the material is uniformly dispersed and there are no particles in the material;

[0062] Cool down to below 50℃, stop vacuum;

[0063] Add dibutyltin dilaurate (0.1%), stir evenly, and then defoam the glue.

[0064] The silane-modified polyether sealant obtained in Examples 6 to 10 and Comparative Examples 4 to 6 was measured for surface dry time, 100% modulus, tensile strength, and elongation at break.

[0065] For surface dry time, the test was performed according to the 8.2B method specified in GB / T 13477.5-2002-“Test Methods for Building Sealant Materials Part 5: Determination of Surface Dry Time”.

[0066] For tensile strength, 100% modulus, and elongation at break, the test was performed according to GB / T 528-2009-“Determination of Tensile Stress-Strain Properties of Vulcanized or Thermoplastic Rubber”.

[0067] The effect data of each example is as follows:

[0068] Data Table Dry Time (min) Strength at 100% (Mpa) Tensile Strength (Mpa) Elongation at Break (%) Example Six 51 0.45 1.22 381 Example Seven 70 0.51 0.96 301 Example Eight 63 0.34 0.7 467 Example Nine 127 0.4 0.67 312 Example Ten 76 0.35 0.9 415 Comparative Example Four 42 0.66 1.1 145 Comparative Example Five 31 0.7 1.5 117 Comparative Example Six 85 0.4 1.12 276

[0069] By reacting the end group NCO in KH540, KH530, KH550 (preferably KH540) and MDI50, a silane with only one NCO group is generated, which can be used for the production of isocyanate silane-modified polyether polymer by end-capping. The produced isocyanate silane-modified polyether polymer resin has higher elongation, and because MDI50 is 2.4-diphenylmethane diisocyanate, the positions of the NCO groups are different, resulting in different activities. The hydrogen group will preferentially react with the more active one of the NCO groups, leaving the other NCO group for the next end-capping reaction. The chain extension phenomenon is not obvious, the reaction is mild and controllable, the chain length is uniform, the product viscosity is low, the production is beneficial, and the elongation is high and the price is cheap.

[0070] In the description of the present application, it should be noted that the terms "upper", "lower", "inner", "outer", "front end", "rear end", "both ends", "one end", "the other end" and the like indicate the orientation or positional relationship based on the orientation or positional relationship shown in the drawings, and are only for the convenience of describing the present application and simplifying the description, and do not indicate or imply that the devices or elements referred to must have a particular orientation, be constructed and operated in a particular orientation, and therefore cannot be understood as limiting the present application. In addition, the terms "first" and "second" are only for descriptive purposes and cannot be understood as indicating or implying relative importance.

[0071] In the description of the present application, it should be noted that unless specifically defined and limited otherwise, the terms "mounting", "provided with", "connected" and the like, should be broadly understood, for example, "connected" can be fixedly connected, or detachably connected, or integrally connected; can be mechanically connected, or electrically connected; can be directly connected, or indirectly connected through an intermediate medium, can be the communication inside two elements. For those skilled in the art, the specific meaning of the above terms in the present application can be understood according to the specific circumstances.

[0072] The above is only the preferred specific embodiment of the present application, but the protection scope of the present application is not limited to this. Any skilled person in the art, according to the technical solution and the inventive concept of the present application, makes equivalent replacement or change within the technical range disclosed by the present application, which should be covered within the protection scope of the present application.

Claims

1. A process for the preparation of an isocyanatosilane-modified polyether polymer, characterized in that, The specific steps are as follows: S1. Slowly drop the amino silane coupling agent into MDI50 in a temperature environment of 40-60℃; S2. Drop for 1-2h, continue to react for 8-16h to obtain isocyanate silane; S3. Dehydrate and degasify the polyether polyol under vacuum at 100-120℃ for 2-3h; S4. Then cool to 70-90℃, add the isocyanate silane in S2 into the polyether polyol, and stir uniformly; S5. Finally, add a catalyst, react at 80-100℃ for 3-8h, then remove the bubbles under vacuum at the reaction temperature to obtain isocyanate silane modified polyether polymer; The molar ratio of isocyanate of MDI50 to amino of amino silane is 1.1-1.5:2; The MDI50 used is 2,4-diphenylmethane diisocyanate.

2. The method of claim 1, wherein the isocyanatosilane-modified polyether polymer is prepared by the reaction of a polyether diol and a diisocyanate in the presence of a catalyst. The polyether polyol has a functionality of 2 or 3 and a number average molecular weight of 4000-18000.

3. The method for preparing an isocyanate-based silane-modified polyether polymer according to claim 1, characterized in that, The catalyst in S5 is dibutyltin dilaurate, stannous octoate or dibutyltin diacetate.

4. The method for preparing an isocyanate-based silane-modified polyether polymer according to claim 1, characterized in that, The amino silane coupling agent used is γ-aminopropyltrimethoxysilane, γ-aminopropyltriethoxysilane or γ-aminopropylmethyldimethoxysilane.

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