CN107698756B - Silane modified linear polyurea adhesive and preparation and application thereof - Google Patents
Silane modified linear polyurea adhesive and preparation and application thereof Download PDFInfo
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- CN107698756B CN107698756B CN201710765284.7A CN201710765284A CN107698756B CN 107698756 B CN107698756 B CN 107698756B CN 201710765284 A CN201710765284 A CN 201710765284A CN 107698756 B CN107698756 B CN 107698756B
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- 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
- C08G71/00—Macromolecular compounds obtained by reactions forming a ureide or urethane link, otherwise, than from isocyanate radicals in the main chain of the macromolecule
- C08G71/02—Polyureas
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J175/00—Adhesives based on polyureas or polyurethanes; Adhesives based on derivatives of such polymers
- C09J175/02—Polyureas
Abstract
The invention discloses a silane modified linear polyurea adhesive and a preparation method and application thereof. According to the preparation method, one or more diamines and excessive aliphatic carbonates are used for preparing terminal carbonate linear polyurea, and then a primary amine silane coupling agent is used for carrying out end capping, so that the silane-terminated linear polyurea adhesive is prepared. The method is simple to operate and pollution-free, the traditional isocyanate is not used for preparing polyurea, the step of preparing diisocyanate by diamine photochemical reaction is omitted, the energy is saved, the synthetic process is mild, a large amount of heat is not released, and a cross-linking structure is not generated in the synthetic process, so that the linear polyurea is easier to prepare. The silane modified linear polyurea sealant is suitable for assembling and bonding automobile windshields.
Description
Technical Field
The invention belongs to the field of organic high polymer materials, and relates to a non-isocyanate silane modified linear polyurea adhesive, a preparation method thereof and application thereof in an automobile windshield sealant formula system.
Background
The polyurethane material has excellent mechanical strength, toughness and wear resistance, and is one of the most widely applied high polymer materials in daily life. The modified polyurethane is mainly prepared by reacting isocyanate and polyol, and has flexible molecular structure design and wide formula performance range. The sealant prepared from polyurethane is one of the sealing materials which are widely applied at present. The polyurethane sealant has excellent mechanical properties and is mainly used for assembling automobile windshields. However, the aging resistance of the polyurethane material is poor, and the aged sealant can not ensure the safety of automobile operation. The adhesion between the polyurethane sealant and common inorganic materials of automobiles such as glass, aluminum materials and the like is poor, the adhesion can be ensured by matching with a special primer when in use, and the construction process is complex. And the raw material for preparing the isocyanate is the highly toxic phosgene, which seriously harms the health of people and has great threat to the environment. And the isocyanate and the polyol react with moisture in the surrounding environment to generate carbon dioxide, so that cells are generated in the material, and the mechanical property of the polyurethane material is reduced. Polyurea is used as one of polyurethane materials, has excellent thermal-oxidative aging resistance compared with the traditional polyurethane materials, is mainly prepared by the reaction of isocyanate and polyamine, but because the reaction of the isocyanate and the polyamine is violent, the reaction process is difficult to control, and the generated carbamido can continuously react with the isocyanate at about 100 ℃ to generate biuret and generate gel, so that linear polyurea molecules are difficult to obtain by the traditional synthetic method.
The silane modified polyurethane adhesive is also called as SPUR adhesive, and mainly comprises siloxane-terminated linear polyurethane (also called as SPUR prepolymer), and the traditional synthesis method comprises the following steps: the polyurethane prepolymer is obtained by adding siloxane containing amino and NCO end-capped polyurethane prepolymer. The molecular structural formula is shown as formula V:
the SPUR adhesive combines the advantages of high elasticity, low-temperature flexibility and cohesiveness of polyurethane and water resistance and heat resistance of organosilicon, and the structure of the SPUR adhesive is regulated and controlled flexibly, but because the urethane group (-NHCOO-) is aged and decomposed by thermal oxidation under the conditions of high temperature (>80 ℃) and oxygen, the SPUR adhesive is not suitable for long-term use under the high-temperature environment, thereby limiting the application range of the SPUR adhesive.
In consideration of the above factors, it is desirable to provide a method for synthesizing a linear polyurea adhesive which does not use isocyanate raw materials and has good thermal-oxidative aging resistance and bonding performance. Recent patents in China report a method for preparing a polyurethane material by using carbonate and polyamine by a non-isocyanate method, wherein the method comprises the following steps:
CN102336891A prepares polyethylene glycol and polypropylene glycol block copolyether diol compound by using polyethylene glycol, propylene oxide and epichlorohydrin, then the polyethylene glycol and polypropylene glycol block copolyether diol compound and dimethyl carbonate are subjected to ester exchange reaction to prepare polyethylene glycol and polypropylene glycol cyclic carbonate, then the polyethylene glycol and polypropylene glycol cyclic carbonate and diamine are subjected to nucleophilic addition reaction to obtain non-isocyanate polyurethane, and then the non-isocyanate polyurethane is added into epoxy resin solution to carry out cross-linking hybridization reaction to obtain the non-isocyanate polyurethane-epoxy resin material, wherein the material does not contain carbamido group, and all obtained by the reaction are carbamate groups, so the material also has the problem that the material cannot be used at high temperature for a long time.
CN102718964A polyether diol, epoxy chloropropane, heterogeneous phase loaded potassium carbonate and potassium iodide are used for preparing polyether dicarbonate, then the polyether dicarbonate is reacted with diamine to obtain non-isocyanate polyurethane, and the non-isocyanate polyurethane is mixed with diphenylmethane diisocyanate component and then sprayed to obtain the non-isocyanate polyurethane spraying polyurea coating film. The patent mainly adopts non-isocyanate polyurethane to replace amine-terminated polyether, and solves the problems of high energy consumption and high pollution in the production of the amine-terminated polyether, so that green chemistry, low-carbon economy and atomic economy are realized, but the patent does not relate to the field of adhesives.
CN104513393A diamine and cyclic carbonate are used to prepare diamine ester diol, which is then subjected to ester exchange reaction with polyether diol in the presence of catalyst to obtain thermoplastic biodegradable poly (ether-urethane). The thermoplastic poly (ether-urethane) material has a large amount of carbamate (-NHCOO-) groups and ester groups (-COO-) so that the thermoplastic poly (ether-urethane) material is difficult to use in a high-temperature (>80 ℃) environment for a long time.
CN104829833A first prepares straight-chain type and ester ring type diamine ester diols with two different diamines and cyclic carbonates, the straight-chain type diamine ester diols are polymerized to prepare prepolymers with different molecular weights, and then the prepolymers are performed with polyether diols and alicyclic type diamine diols to perform urethane exchange reaction in the presence of catalysts, so as to obtain biodegradable crystalline thermoplastic poly (ether urethanes) and elastomers. The existence of a large amount of carbamate (-NHCOO-) groups and ester groups (-COO-) in the biodegradable crystalline thermoplastic poly (ether urethane) and the elastomer makes the biodegradable crystalline thermoplastic poly (ether urethane) difficult to use in a high-temperature (>80 ℃) environment for a long time.
US9012676B2 describes the carbonylation of aromatic polyamines with diphenyl carbonate to give aromatic carbamates which are thermally cracked at 200-230 ℃ to give 4, 4' -diphenylmethane diisocyanate (MDI), and the reaction of the dibasic carbamates with one or more amines to give high molecular weight polyurea elastomers. This patent is primarily concerned with the non-isocyanate process for the production of MDI monomers and high molecular weight polyurea elastomers.
The non-isocyanate method silane modified linear polyurea adhesive disclosed by the invention does not use an isocyanate monomer with high toxicity and humidity sensitivity in the preparation process, but uses carbonate, diamine and a silane coupling agent, so that the requirement of the state on a clean production process is met, and the raw material cost of the product is reduced; and the system does not contain urethane groups (-NHCOO-), and urea groups are replaced by the urea groups, so that the urea groups have higher thermal oxygen stability than the urethane groups, and the hydrogen bond content in the adhesive system is increased by the presence of the urea groups, so that the thermal oxygen aging resistance of the adhesive and the bonding property with a substrate are improved. Thereby improving the service life of the adhesive under the high temperature condition.
Disclosure of Invention
The embodiment of the invention aims to provide a non-isocyanate silane modified linear polyurea adhesive, a preparation method thereof and application thereof in a sealant formula, aiming at solving the problems that high-toxicity isocyanate is used in the synthesis process of the traditional silane modified polyurethane adhesive and the traditional silane modified polyurethane adhesive can not be used for a long time under the condition of high temperature (80 ℃).
According to a first aspect of the present invention, there is provided a non-isocyanate silane-modified linear polyurea adhesive, i.e. a silicone-terminated linear polyurea adhesive, obtained by: dropwise adding one or more than one diamine into an excessive (for example, according to a molar ratio of 1: 1.5-2) aliphatic linear carbonate system at the temperature of 60-160 ℃ (preferably 80-140 ℃), and reacting to obtain carbonate-terminated linear polyurea; and then reacting the carbonate-terminated linear polyurea with a primary amino silane coupling agent at the temperature of 80-150 ℃ (preferably 80-130 ℃) to obtain the siloxane-terminated linear polyurea adhesive.
Further, the silane-modified linear polyurea adhesive has the general formula:
(R4O)3SiR3NH[C(O)NHR2NHC(O)NHR2NH]mC(O)NHR3Si(OR4)3
(I)
in the formula R2Selected from C1-C10 alkylene, C3-C16 cycloalkylene, C3-C16 ether, preferably C3-C12 cycloalkylene, C3-C16 ether, more preferably C3-C12 ether;
further preferred is R2Is composed of
Wherein n is an integer from 1 to 8, preferably from 1 to 6, more preferably from 1 to 4;
R3selected from C1-C10 alkylene, preferably C3-C5 alkylene; r4Selected from C1-C10 alkylene, preferably C1-C4 alkylene; m is an integer of 1 to 40, preferably 1 to 10, more preferably 1 to 3.
In order to achieve the purposes, the invention adopts a method for preparing the silane modified linear polyurea adhesive by a non-isocyanate method, which comprises the following specific steps:
1) at a certain temperature, one or more than one diamine is/are dripped into an excessive aliphatic linear carbonate system according to a certain molar ratio, the temperature of the reaction system is raised for reaction after the dripping is finished, and then generated alcohols and water are removed to obtain carbonate-terminated linear polyurea;
2) at a certain temperature, after the carbonate-terminated linear polyurea obtained in the step 1) is mixed with a primary amino silane coupling agent, the temperature of a reaction system is raised for reaction, and then alcohols and water generated in the system are removed to obtain the siloxane-terminated linear polyurea adhesive.
Wherein the aliphatic linear carbonate used in step 1) has a structure represented by the general formula (I):
in the above formula, R1Is a C1-C10 aliphatic radical, preferably a C1-C6 aliphatic radical, e.g. -CH3，-CH2CH3And the like.
Wherein, the diamine used in the step 1) has a structure shown in a general formula (III):
in the above formula, R2Selected from C1-C10 alkylene, C3-C16 cycloalkylene, C3-C16 ether, preferably C3-C12 cycloalkylene, C3-C16 ether, more preferably C3-C12 ether;
further preferred is R2Is composed of
The general formula of the primary amino silane coupling agent used in the step 2) is as follows:
(R4O)3SiR3NH2
(IV)
R3selected from C1-C10 alkylene, preferably C3-C5; r4Selected from C1-C10 alkylene, preferably C1-C4, more preferably R3is-CH2CH2CH2-，R4is-C2H5-or-CH3Namely: 3-aminopropyltriethoxysilane (KH550) and 3-aminopropyltrimethoxysilane (KH 540).
The certain temperature is 80-120 ℃, preferably 85-95 ℃ or 85-100 ℃.
Preferably, step 1) is performed as follows: dropwise adding one or more than one diamine into an excessive aliphatic linear carbonate system according to a molar ratio of 1: 1.5-2, preferably 1: 1.6-1.8 at 80-100 ℃, preferably 85-95 ℃ under the protection of nitrogen, raising the temperature of the reaction system to 120-140 ℃, preferably 125-135 ℃ after dropwise adding, reacting for 8-20h, preferably 10-12 h, and then removing generated alcohols and water in vacuum to obtain the linear polyurea terminated by carbonate.
Preferably, step 2) is performed as follows: feeding the carbonate-terminated linear polyurea obtained in the step 1) and a primary amino silane coupling agent according to a molar ratio of 1: 1-1.2, preferably 1: 1-1.05, under the protection of nitrogen at 80-120 ℃, preferably 80-100 ℃, mechanically mixing for 1-3 hours, preferably about 2 hours, raising the temperature of the system to 120-140 ℃, preferably 120-130 ℃, reacting for 8-12 hours, preferably 9-11 hours, and then removing alcohols and water generated in the system in vacuum to obtain the siloxane-terminated linear polyurea adhesive.
The carbonate-terminated linear polyurea obtained in step 1) has a structure represented by the general formula (VI):
R1O[C(O)NHR2NHC(O)NHR2NH]mC(O)OR1
(VI)
in the formula R1Is a C1-C10, preferably C1-C6 aliphatic radical, e.g. -CH3，-CH2CH3An aliphatics group;
R2selected from C1-C10 alkylene, C3-C16 cycloalkylene, C3-C16 ether, preferably C3-C12 cycloalkylene, C3-C16 ether, more preferably C3-C12 ether;
further preferred is R2Is composed of
Wherein n is an integer from 1 to 8, preferably from 1 to 6, more preferably from 1 to 4;
the siloxane-terminated linear polyurea obtained in step 2) has the structure shown in the general formula (I):
(R4O)3SiR3NH[C(O)NHR2NHC(O)NHR2NH]mC(O)NHR3Si(OR4)3
(I)
in the formula R2Selected from C1-C10 alkylene, C3-C16 cycloalkylene, C3-C16 ether, preferably C3-C12 cycloalkylene, C3-C16 ether, more preferably C3-C12 ether;
further preferred is R2Is composed of
Wherein n is an integer from 1 to 8, preferably from 1 to 6, more preferably from 1 to 4;
R3selected from C1-C10 alkylene, preferably C3-C5 alkylene; r4Selected from C1-C10 alkylene, preferably C1-C4 alkylene; m is an integer of 1 to 40, preferably 1 to 10, more preferably 1 to 3.
The siloxane-terminated linear polyurea system obtained in the step 2) contains a large amount of carbamido groups, hydrogen bonds are easy to generate, and the viscosity of the resin is increased, so that the viscosity of the synthesized linear polyurea is 100cp-50000cp, and preferably 100cp-30000 cp.
The invention also provides an automobile windshield assembly sealant comprising the siloxane-terminated linear polyurea adhesive. The sealant may also include conventional components such as plasticizers, e.g., diisodecyl phthalate, fillers, e.g., silica, titanium dioxide, calcium carbonate, etc., silane adhesion promoters, catalysts, e.g., dibutyltin dilaurate, etc.
The invention further provides application of the siloxane-terminated linear polyurea adhesive in preparing an automobile windshield assembly sealant.
The invention has the beneficial effects that:
(1) the synthesis process of the silane modified linear polyurea adhesive prepared by the invention does not use isocyanate monomers with high toxicity and humidity sensitivity, but uses carbonic ester, diamine and silane coupling agent, thereby meeting the national requirement on clean production process and reducing the raw material cost of the product.
(2) The linear polyurea molecule synthesized by the method has a simpler synthesis process than the traditional diamine and diisocyanate, the molecular weight is easier to control, and a large amount of heat is not released in the synthesis process, so that a cross-linking structure is not generated.
(3) The silane modified linear polyurea system does not contain carbamate (-NHCOO-), and urea groups are replaced, so that the urea groups have higher thermal oxidation stability than the carbamate groups, and the hydrogen bond content in the adhesive system is increased due to the urea groups, so that the high-temperature-resistant service performance of the adhesive is improved.
(4) The existence of carbamido increases the hydrogen bond content in the adhesive system, thereby improving the bonding property of the adhesive and the base material.
Detailed Description
The present invention is further illustrated by the following specific examples, which are intended to be illustrative only and not to limit the scope of the invention.
The raw materials and sources are detailed in table 1.
TABLE 1 raw materials and sources
Example 1
(1) Preparation of terminal carbonate Linear polyurea: dissolving 0.02mol HDA into 0.02mol IPDA at 90 ℃ under the protection of nitrogen, then slowly dripping into a 0.072mol diethyl carbonate system, raising the temperature of the reaction system to 120 ℃ after finishing dripping, continuously reacting for 10h, and then removing generated ethanol and water in vacuum to obtain the carbonate-terminated linear polyurea.
(2) Preparation of siloxane-terminated linear polyurea adhesive: adding 0.021mol of 3-aminopropyltriethoxysilane (KH550) into the linear polyurea which is terminated by carbonic ester and obtained in the previous step at 100 ℃ under the protection of nitrogen, mechanically mixing for 2h, raising the temperature of a reaction system to 120 ℃, and continuously reacting for 10 h. And then removing ethanol generated in the system in vacuum to obtain the siloxane-terminated linear polyurea adhesive SPUA 1.
Example 2
(1) Preparation of terminal carbonate Linear polyurea: slowly dripping 0.03mol of IPDA and 0.01mol of polyetheramine (D230) into a 0.072mol of diethyl carbonate system at 90 ℃ under the protection of nitrogen, raising the temperature of the reaction system to 120 ℃ after finishing dripping, continuously reacting for 10h, and then removing generated ethanol and water in vacuum to obtain the linear polyurea of the carbonic ester end capping.
(2) Preparation of siloxane-terminated linear polyurea adhesive: adding 0.021mol of 3-aminopropyltriethoxysilane (KH550) into the linear polyurea system terminated by carbonate obtained in the previous step at 100 ℃ under the protection of nitrogen, mechanically mixing for 2h, raising the temperature of the reaction system to 120 ℃, and continuing to react for 10 h. And then removing ethanol generated in the system in vacuum to obtain the siloxane-terminated linear polyurea adhesive SPUA 2.
Example 3
(1) Preparation of terminal carbonate Linear polyurea: dissolving 0.02mol of HDA into 0.02mol of 1, 3-propane diamine under the protection of nitrogen at 90 ℃, then slowly dropwise adding into a 0.072mol of diethyl carbonate system, raising the temperature of the reaction system to 120 ℃ after the dropwise adding is finished, continuously reacting for 10h, and then removing the generated ethanol and water in vacuum to obtain the carbonate-terminated linear polyurea.
(2) Preparation of siloxane-terminated linear polyurea adhesive: adding 0.021mol of 3-aminopropyltriethoxysilane (KH550) into the linear polyurea system terminated by carbonate obtained in the previous step at 100 ℃ under the protection of nitrogen, mechanically mixing for 2h, raising the temperature of the reaction system to 120 ℃, and continuing to react for 10 h. And then removing ethanol generated in the system in vacuum to obtain the siloxane-terminated linear polyurea adhesive SPUA 3.
Example 4
(1) Preparation of terminal carbonate Linear polyurea: slowly dripping 0.02mol of 1,3-BAC and 0.02mol of 1, 3-propane diamine into a 0.072mol of diethyl carbonate system at 90 ℃ under the protection of nitrogen, raising the temperature of the reaction system to 120 ℃ after finishing dripping, continuously reacting for 10h, and then removing generated ethanol and water in vacuum to obtain the carbonate-terminated linear polyurea.
(2) Preparation of siloxane-terminated linear polyurea adhesive: adding 0.021mol of 3-aminopropyl trimethoxy silane (KH540) into the linear polyurea system terminated by carbonate obtained in the previous step at 100 ℃ under the protection of nitrogen, mechanically mixing for 2h, raising the temperature of the reaction system to 120 ℃, and continuing to react for 10 h. And then removing ethanol generated in the system in vacuum to obtain the siloxane-terminated linear polyurea adhesive SPUA 4.
Example 5
(1) Preparation of terminal carbonate Linear polyurea: slowly dripping 0.02mol of 1,3-BAC and 0.02mol of HDA into a 0.072mol of diethyl carbonate system at 90 ℃ under the protection of nitrogen, raising the temperature of the reaction system to 120 ℃ after finishing dripping, continuously reacting for 10h, and then removing generated ethanol and water in vacuum to obtain the linear polyurea of the end capping of the carbonic ester.
(2) Preparation of siloxane-terminated linear polyurea adhesive: adding 0.021mol of 3-aminopropyl trimethoxy silane (KH540) into the linear polyurea system terminated by carbonate obtained in the previous step at 100 ℃ under the protection of nitrogen, mechanically mixing for 2h, raising the temperature of the reaction system to 120 ℃, and continuing to react for 10 h. And then removing ethanol generated in the system in vacuum to obtain the siloxane-terminated linear polyurea adhesive SPUA 5.
Example 6
(1) Preparation of terminal carbonate Linear polyurea: slowly dripping 0.02mol of 1,3-BAC and 0.02mol of 1, 4-butanediamine into a 0.08mol of dimethyl carbonate system at 90 ℃ under the protection of nitrogen, raising the temperature of the reaction system to 120 ℃ after finishing dripping, continuously reacting for 10h, and then removing generated methanol and water in vacuum to obtain the linear polyurea of the carbonate end capping.
(2) Preparation of siloxane-terminated linear polyurea adhesive: adding 0.021mol of 3-aminopropyl trimethoxy silane (KH540) into the linear polyurea system terminated by carbonate obtained in the previous step at 100 ℃ under the protection of nitrogen, mechanically mixing for 2h, raising the temperature of the system to 120 ℃, and continuing to react for 10 h. And then removing the methanol generated in the system in vacuum to obtain the siloxane-terminated linear polyurea adhesive SPUA 6.
Example 7
(1) Preparation of terminal carbonate Linear polyurea: slowly dripping 0.02mol of HMDA and 0.02mol of 1, 3-propane diamine into a 0.08mol of dimethyl carbonate system at 90 ℃ under the protection of nitrogen, raising the temperature of the reaction system to 120 ℃ after finishing dripping, continuously reacting for 10h, and then removing generated methanol and water in vacuum to obtain the linear polyurea of the carbonate end capping.
(2) Preparation of siloxane-terminated linear polyurea adhesive: adding 0.021mol of 3-aminopropyl trimethoxy silane (KH540) into the linear polyurea system terminated by carbonate obtained in the previous step at 100 ℃ under the protection of nitrogen, mechanically mixing for 2h, raising the temperature of the system to 120 ℃, and continuing to react for 10 h. And then removing the methanol generated in the system in vacuum to obtain the siloxane-terminated linear polyurea adhesive SPUA 7.
Comparative example
A siloxane-terminated linear polyurethane adhesive was prepared as follows:
(1) preparing an isocyanate-terminated prepolymer: slowly and dropwise adding 0.04mol of 1, 4-butanediol into a system of 0.04mol of IPDI, 0.04mol of HDI and 0.0001mol of dibutyltin dilaurate at the temperature of 70 ℃ under the protection of nitrogen, raising the temperature of the reaction system to 90 ℃ after dropwise adding is finished, and continuously reacting for 10 hours to obtain the isocyanate-terminated prepolymer.
(2) Preparation of siloxane-terminated linear polyurethane adhesive: slowly dripping 0.021mol of secondary amino silane coupling agent SILQUESTY-9669 into the isocyanate-terminated prepolymer obtained in the previous step under the conditions of 70 ℃, nitrogen protection and mechanical mixing, raising the temperature of the system to 90 ℃, continuing to react for 10 hours, and removing vacuum to obtain the siloxane-terminated linear polyurethane adhesive-SPUR.
The viscosities of the SPUA and the SPUR prepared in the examples of the present invention were measured using a United states Bohler viscometer, and the application properties in the sealant were compared according to the following formulation:
the formulation system is referred to the following table:
| components | Weight (D) |
| SPUA/SPUR | 250 |
| Diisodecyl Phthalate (DIDP) | 100 |
| Silquest A-171 silane | 5 |
| Calcium carbonate (thin) | 150 |
| Calcium carbonate (coarse) | 100 |
| TiO2 | 7.5 |
| SiO2 | 15 |
| Silquest silane adhesion promoter | 3.75 |
| Organotin compounds | 0.5 |
And (3) mixing the components at 60 ℃ for 1h to obtain the corresponding sealant. The surface drying time of the sealant and the bonding strength of the sealant and a glass substrate are tested according to national standards, then the sealant is vulcanized for three days in an indoor environment with the temperature of 23 ℃ and the relative humidity of 50 percent, the cured sample strip is prepared by vulcanizing in a common oven for 4 days at the temperature of 50 ℃, the sample strip is tested according to the corresponding national standards and standards, and then the performance of the sample strip is tested again after thermal oxidation aging is carried out for 300 hours at the temperature of 90 ℃. The test criteria are as follows: peel strength (GB/T2790-:
TABLE 2
As can be seen from table 2, the SPUA sealant has relatively longer surface dry time, higher peel strength, tensile strength and hardness, and lower elongation at break than the SPUR sealant, but the tensile strength, elongation at break and hardness before and after aging of the SPUA sealant change less, and shows better resistance to thermal oxidative aging. Therefore, the siloxane-terminated linear polyurea adhesive prepared by the non-isocyanate method not only meets the national requirement on a clean production process and reduces the raw material cost of the product, but also has more excellent thermal and oxygen resistance compared with the traditional siloxane modified polyurethane adhesive.
Claims (15)
1. A silane-modified linear polyurea adhesive obtained by the steps of: one or more than one diamine is dripped into an excessive aliphatic linear carbonate system to react at elevated temperature to obtain carbonate-terminated linear polyurea, and then the carbonate-terminated linear polyurea and a primary amino silane coupling agent react at elevated temperature to obtain the siloxane-terminated linear polyurea adhesive.
2. The silane-modified linear polyurea adhesive of claim 1 having the general formula:
(R4O)3SiR3NH[C(O)NHR2NHC(O)NHR2NH]mC(O)NHR3Si(OR4)3
(I)
in the formula R2Selected from C1-C10 alkylene, C3-16 cycloalkylene, C3-C16 ether;
R3selected from C1-C10 alkylene;
R4selected from C1-C10 alkylene;
m is an integer of 1 to 40.
3. The silane-modified linear polyurea adhesive of claim 2 wherein R2Selected from C1-C10 alkylene, C3-C12 cycloalkylene, C3-C12 ether; r3Selected from C3-C5 alkylene; r4Selected from C1-C4 alkylene; m is an integer of 1 to 10.
4. The silane-modified linear polyurea adhesive of claim 2, wherein:
R2is composed of
Wherein n is an integer from 1 to 8.
5. A process for preparing the silane-modified linear polyurea adhesive according to any one of claims 1 to 4, comprising the steps of:
1) one or more than one diamine is dripped into an excessive aliphatic linear carbonate system, the temperature of the reaction system is raised after the dripping is finished, the reaction is carried out, and then generated alcohols and water are removed to obtain carbonate-terminated linear polyurea;
2) mixing the linear polyurea terminated by the carbonic ester obtained in the step 1) with a primary amino silane coupling agent, reacting at elevated temperature, and then removing alcohols and water generated in the system to obtain the linear polyurea adhesive terminated by the siloxane.
6. The method according to claim 5, wherein the aliphatic linear carbonate used in step 1) has a structure represented by general formula (I):
in the above formula, R1Is a C1-C10 aliphatic radical;
wherein, the diamine used in the step 1) has a structure shown in a general formula (III):
H2N-R2-NH2
(III)
in the above formula, R2Selected from C1-C10 alkylene, C3-16 cycloalkylene or C3-C16 ether;
the general formula of the primary amino silane coupling agent used in the step 2) is as follows:
(R4O)3SiR3NH2
(IV)
R3selected from C1-C10 alkylene;
R4selected from C1-C10 alkylene.
7. The method of claim 6, wherein R1Is a C1-C6 aliphatic radical;
R2selected from C1-C10 alkylene, C3-C12 cycloalkylene, C3-C12 ether;
R3selected from C3-C5 alkylene;
R4selected from C1-C4 alkylene.
8. The method of claim 6, wherein
R2Is composed of
9. The method of claim 6, wherein R3is-CH2CH2CH2-，R4is-C2H5-or-CH3。
10. The method according to any one of claims 5 to 9, wherein the diamine is added dropwise to the excess aliphatic linear carbonate system in a diamine to aliphatic linear carbonate molar ratio of 1:1.5 to 2.
11. The method according to any one of claims 5-9, wherein step 1) is performed as follows: dropwise adding one or more than one diamine into an excessive aliphatic linear carbonate system according to the molar ratio of 1: 1.5-2 at 80-100 ℃ under the protection of nitrogen, raising the temperature of the reaction system to 120-140 ℃ after dropwise adding, reacting for 8-20h, and then removing generated alcohol and water in vacuum to obtain the carbonate-terminated linear polyurea.
12. The method according to any one of claims 5-9, wherein the carbonate terminated linear polyurea in step 2) is present in a molar ratio of 1:1 to 1.2 relative to the primary aminosilane coupling agent.
13. The method according to any one of claims 5-9, wherein step 2) is performed as follows: feeding the carbonate-terminated linear polyurea obtained in the step 1) and a primary amino silane coupling agent according to a molar ratio of 1: 1-1.2 at 80-100 ℃ under the protection of nitrogen, mixing for 1-3 hours, raising the temperature of the system to 120-130 ℃ for reaction for 10-12 hours, and then removing alcohols and water generated in the system in vacuum to obtain the siloxane-terminated linear polyurea adhesive.
14. An automotive windshield assembly sealant comprising the silane-modified linear polyurea adhesive of any one of claims 1-4.
15. The silane-modified linear polyurea adhesive according to any one of claims 1 to 4 used in the preparation of automotive windshield assembly sealants.
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| CN110760047B (en) * | 2018-07-26 | 2022-04-19 | 万华化学集团股份有限公司 | Bis-secondary amine containing siloxane group and preparation method and application thereof |
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| CN1902259A (en) * | 2003-11-04 | 2007-01-24 | 巴斯福股份公司 | Highly functional, highly branched polyureas |
| CN104327708A (en) * | 2014-10-25 | 2015-02-04 | 重庆市旭星化工有限公司 | Synthesis method of NIPU oligomer coating |
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| CN104327708A (en) * | 2014-10-25 | 2015-02-04 | 重庆市旭星化工有限公司 | Synthesis method of NIPU oligomer coating |
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Denomination of invention: Silane modified linear polyurea adhesive and its preparation and Application Effective date of registration: 20211123 Granted publication date: 20201124 Pledgee: Bank of China Limited by Share Ltd. Yantai branch Pledgor: Wanhua Chemical Group Co.,Ltd. Registration number: Y2021980013026 |
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