Novel diallyl-terminated polyether as well as synthesis method and application thereof

Abstract

The invention relates to the technical field of polymer synthesis, in particular to novel diallyl terminated polyether as well as a synthesis method and application thereof. Aiming at the limitation of the existing material, an acid-base pair catalytic system is used for catalyzing the homopolymerization of an epoxy monomer in the presence of an initiator, and on the basis of the reaction, AGE is added for one-pot reaction to obtain a series of diallyl terminated polyethers with adjustable molecular weight, controllable molecular weight distribution and good polymerization reaction selectivity. And a preparation method and a polymerization process for preparing the diallyl terminated polyether are greatly expanded. The catalytic system has the advantages of being simple in preparation, high in activity, convenient to use, low in cost and wide in universality, and a novel method is provided for preparing special electronic products based on novel diallyl terminated polyether.

Description

Technical Field

[0001] This invention relates to the field of polymer synthesis technology, and in particular to a novel dielyl-terminated polyether, its synthesis method, and its application. Background Technology

[0002] The information disclosed in the background section of this invention is intended only to enhance the understanding of the overall background of the invention and is not necessarily to be construed as an admission or in any way implying that such information constitutes prior art known to those skilled in the art.

[0003] Diallyl-terminated polyether is a chemical intermediate with allyl active groups at both ends. As an ideal crosslinking agent in polymerization reactions, it has important applications in the organosilicon industry. Diallyl-terminated polyether can adapt to different performance requirements by controlling its chain segment structure. Its application value is mainly reflected in the following aspects: (1) Silicone sealant: Through the hydrosilylation reaction of high molecular weight diallyl polyether polyol, organosilicon modified polyether polyol can be obtained, which becomes one of the key components of silicone sealant for building. It is suitable for dynamic joints of wall base-metal, static joints of subway tunnels, as well as static sealing of ordinary roads, large buildings and filling of vibration parts such as bridges; (2) Building sealant: After hydrosilylation modification, high molecular weight diallyl-terminated polyether can be obtained as organosilicon modified polyether, which becomes an important raw material for high performance building sealant; (3) Water reducing agent: Diallyl polyether is introduced into polycarboxylic acid The water-reducing agent system, or its copolymerization with unsaturated fatty acids and allyl polyoxyethylene ether to form a network macromolecular structure, can significantly enhance the viscosity-reducing performance of the water-reducing agent; (4) Adhesion performance: Silane-modified polyether sealant has excellent adhesion and exhibits good adhesion to various substrates such as metal, plastic, and concrete; (5) Green and environmentally friendly characteristics: This type of sealant does not contain toxic solvents such as formaldehyde and toluene, nor does it contain isocyanate groups. Its volatile organic compound (VOC) content is low, and there is no risk of free silicon and silicone oil precipitation. It does not pollute or corrode the substrate; (6) High elasticity and weather resistance: Its main chain is a flexible polyether chain segment, which can withstand large dynamic loads and effectively adapt to the expansion and contraction deformation caused by temperature changes or substrate displacement. The Si-O-Si structure formed after curing gives the material stronger UV resistance and weather resistance. Therefore, the surface cracking phenomenon is much less than that of polyurethane sealant in long-term use.

[0004] There are two main traditional synthetic routes for dielyl-terminated polyethers: The first method involves reacting allyl chloride / dihaloalkane with high molecular weight polyether.

[0005] or ; The second option: using a chain extension reaction. or

[0006] or .

[0007] Existing synthetic routes suffer from problems such as low atom utilization, post-modification, metal ion removal, and the formation of metal salt byproducts, making it difficult to meet the current synthetic principles of green and sustainable development. Therefore, it is crucial to find a green, simple, and sustainable catalyst and synthetic route for the synthesis of dielyl polyethers. Summary of the Invention

[0008] In view of this, the present invention provides a novel diallyl-terminated polyether, its synthesis method, and its application. The technical solution of the present invention uses a Lewis base and a polynuclear organoboron to synthesize diallyl-terminated polyether, which not only simplifies the synthesis steps and eliminates byproducts, but also overcomes the problems of residual metal ions in alkoxide catalysts and the need for their removal in previous synthesis routes.

[0009] To achieve the above objectives, the present invention is implemented through the following technical solution: In a first aspect, the present invention provides a novel dielyl-terminated polyether, the structure of which is shown in formulas (I) and (II): or

[0010] Formula (I) Formula (II) Where n is any positive integer from 20 to 210; m is any positive integer from 1 to 210.

[0011] Secondly, the present invention provides a method for synthesizing the above-mentioned novel dielyl-terminated polyether, comprising the following steps: (1) The catalyst, initiator and epoxy monomer are added to the reaction apparatus in sequence, and the reaction is carried out for 1.5-18 h after sealing to obtain monoallyl-terminated polyether; the catalyst is a mixture of polynuclear organoboron Lewis acid and Lewis base to obtain an acid-base pair; (2) Add allyl glycidyl ether (AGE) to the generated monoallyl-terminated polyether, seal and react for 2-24 h to obtain dielyl-terminated polyether; The reaction route is as follows: ; ; Where n is any positive integer from 20 to 210; m is any positive integer from 1 to 210.

[0012] The synthesis method of this invention uses epoxy monomers and AGE as monomer raw materials. Under initiator conditions, an acid-base catalytic system is used to catalyze the homopolymerization of epoxy monomers and AGE to obtain a series of diallyl-terminated polyethers with adjustable molecular weight and controllable molecular weight distribution and good polymerization selectivity. Under mild conditions (room temperature / normal pressure), diallyl-terminated polyethers are synthesized in a one-pot two-step process. Intermediate products can directly enter the next step of the reaction without separation, which can improve production efficiency and reduce by-reaction products and ion removal problems.

[0013] Preferably, in step (1), the epoxy monomer is propylene oxide (PO) or a mixture of propylene oxide and ethylene oxide (EO). Further, when the epoxy monomer is PO, the product is a diallyl-terminated polyether of formula (I); when the epoxy monomer is a mixture of PO and EO, the product is a diallyl-terminated polyether of formula (II).

[0014] Preferably, in step (1), the molar ratio of epoxy monomer, initiator, Lewis acid and Lewis base is (6000~20000):(30~300):1:1.

[0015] Preferably, in step (1), when the epoxy monomers are PO and EO, the molar ratio of PO to EO is 1-10:1; more preferably 1-6:1; and more preferably 2:1.

[0016] Preferably, in step (1), the reaction is stirred using a magnetic stirrer.

[0017] Preferably, in step (1), the reaction temperature is 20-25℃ and the reaction pressure is atmospheric pressure.

[0018] Preferably, in step (1), the initiator is allyl alcohol or low molecular weight allyl-terminated polypropylene oxide. (Number average molecular weight is 100-500 g / mol).

[0019] Preferably, the polynuclear organoboron Lewis acid is: or or or ; Among them, BY2 is selected independently. , , , or ; R1 is independently selected from hydrogen, halogen, and optionally substituted straight-chain or branched C1-C8 alkyl, C1-C8 alkoxy, C1-C8 alkenyl, C1-C8 alkynyl, and optionally substituted aromatic, fused-ring aromatic or C3-C8 heterocyclic groups. The substituent is selected from halogens, C1-C... 10 Alkyl, halogenated C1-C 10 Alkyl, C1-C 10 The group may be alkoxy, hydroxy, cyano, nitro, amino, or aromatic; the heteroatom in the C3-C8 heterocyclic group may be selected from oxygen, sulfur, or nitrogen. x is any positive integer from 3 to 5000, y is any positive integer from 3 to 5000, h is any positive integer from 1 to 20, and z is any positive integer from 1 to 5.

[0020] More preferably, the polynuclear organoboron Lewis acid is , , or .

[0021] The Lewis base is , Potassium tert-butoxide or potassium methoxide.

[0022] Further, in step (1), the acid-base pair is preferably: or or or or or

[0023] or .

[0024] The Lewis acid-base pair, when used in the preparation of polyethers in the presence of an initiator, can control the molecular weight of the polyether (high or low molecular weight polyethers) and reduce the molecular weight distribution of the polyether.

[0025] Preferably, in step (2), the reaction temperature is 20-25℃ and the reaction pressure is atmospheric pressure.

[0026] Preferably, in step (2), the reaction time is 2-12 h; more preferably, it is 2-6 h.

[0027] Preferably, in step (2), the molar ratio of AGE to initiator is 1:1-1.2.

[0028] Preferably, in step (2), the molecular weight of the dielyl-terminated polyether is 0.6-22 kg / mol and the molecular weight distribution is ≤1.10.

[0029] Thirdly, the present invention provides the application of the diallyl-terminated polyether described in the first aspect in the fields of special electronic products, elastomers, and coatings.

[0030] Compared with the prior art, the present invention has achieved the following beneficial effects: (1) The method for synthesizing diallyl-terminated polyether provided by the present invention can synthesize diallyl-terminated polyether in one pot under mild conditions (room temperature / normal pressure), which can improve production efficiency, reduce by-reaction products and ion removal problems, achieve cost reduction and efficiency improvement, and greatly expand the application of this type of material in many fields including special electronic products, elastomers and coatings.

[0031] (2) The synthesis method provided by the present invention uses an acid-base catalytic system obtained under initiator conditions to catalyze the homopolymerization of epoxy monomers, thereby obtaining a series of diallyl-terminated polyethers with adjustable molecular weight and controllable molecular weight distribution and good polymerization selectivity, which greatly expands the preparation method and polymerization process of diallyl-terminated polyethers. Attached Figure Description

[0032] The accompanying drawings, which form part of this invention, are used to provide a further understanding of the invention. The illustrative embodiments of the invention and their descriptions are used to explain the invention and do not constitute an improper limitation of the invention.

[0033] Figure 1 The novel monoallyl-terminated polyether prepared in Example 1 1 H NMR spectrum; Figure 2 GPC diagram of the novel monoallyl-terminated polyether prepared in Example 1; Figure 3 The novel dielyl-terminated polyether prepared in Example 1 1 H NMR spectrum; Figure 4 GPC diagram of the novel dielyl-terminated polyether prepared in Example 1; Figure 5 The novel monoallyl-terminated polyether prepared in Example 2 1 H NMR spectrum; Figure 6 GPC diagram of the novel monoallyl-terminated polyether prepared in Example 2; Figure 7 The novel dielyl-terminated polyether prepared in Example 2 1 H NMR spectrum; Figure 8 GPC diagram of the novel dielyl-terminated polyether prepared in Example 2; Figure 9 The novel monoallyl-terminated polyether prepared in Example 31 H NMR spectrum; Figure 10 GPC diagram of the novel monoallyl-terminated polyether prepared in Example 3; Figure 11 The novel dielyl-terminated polyether prepared in Example 3 1 H NMR spectrum; Figure 12 GPC diagram of the novel dielyl-terminated polyether prepared in Example 3; Figure 13 The novel monoallyl-terminated polyether prepared in Example 4 1 H NMR spectrum; Figure 14 GPC diagram of the novel monoallyl-terminated polyether prepared in Example 4; Figure 15 The novel dielyl-terminated polyether prepared in Example 4 1 H NMR spectrum; Figure 16 GPC diagram of the novel dielyl-terminated polyether prepared in Example 4; Figure 17 The novel monoallyl-terminated polyether prepared in Example 5 1 H NMR spectrum; Figure 18 GPC diagram of the novel monoallyl-terminated polyether prepared in Example 5; Figure 19 The novel dielyl-terminated polyether prepared in Example 5 1 H NMR spectrum; Figure 20 GPC diagram of the novel dielyl-terminated polyether prepared in Example 5; Figure 21 The novel monoallyl-terminated polyether prepared in Example 6 1 H NMR spectrum; Figure 22 GPC diagram of the novel monoallyl-terminated polyether prepared in Example 6; Figure 23 The novel dielyl-terminated polyether prepared in Example 6 1 H NMR spectrum; Figure 24 GPC diagram of the novel dielyl-terminated polyether prepared in Example 6; Figure 25 The novel monoallyl-terminated polyether prepared in Example 7 1 H NMR spectrum; Figure 26 GPC diagram of the novel monoallyl-terminated polyether prepared in Example 7; Figure 27 The novel dielyl-terminated polyether prepared in Example 7 1 H NMR spectrum; Figure 28 GPC diagram of the novel dielyl-terminated polyether prepared in Example 7; Figure 29 The novel monoallyl-terminated polyether prepared in Example 8 1 H NMR spectrum; Figure 30 GPC diagram of the novel monoallyl-terminated polyether prepared in Example 8; Figure 31 The novel dielyl-terminated polyether prepared in Example 8 1 H NMR spectrum; Figure 32 The image shows the GPC diagram of the novel dielyl-terminated polyether prepared in Example 8. Detailed Implementation

[0034] It should be noted that the following detailed descriptions are exemplary and intended to provide further illustration of the invention. Unless otherwise specified, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention pertains.

[0035] The technical solution of the present invention will be further described below with reference to specific embodiments.

[0036] Example 1 In a glove box, POSS-B8 (5 μmol, 8 mg, 1 equivalent), TBASA (5 μmol, 3 mg, 1 equivalent), allyl alcohol (1.5 mmol, 100 μL, 300 equivalent), and PO (30 mmol, 2.1 mL, 6000 equivalent) were sequentially added to a pre-flame-dried 15 mL pressure-resistant bottle containing a magnetic magnet. The pressure-resistant bottle was sealed and removed from the glove box. The reaction time was controlled at 3 h, and the reaction temperature was 25 °C, yielding a monoallyl-terminated polyether. GPC analysis showed a number-average molecular weight (Mn) of 1 kg / mol and a molecular weight distribution of... The molecular weight was 1.07. After obtaining the monoallyl-terminated polyether, AGE (1.5 mmol, 178 μL, 300 equivalents) was added, and the reaction time was controlled at 2 h and the reaction temperature at 25 °C to obtain the dielyl-terminated polyether. The number-average molecular weight was measured by GPC. Mn It is 1.2 kg / mol, and the molecular weight distribution is... The value is 1.07. The monoallyl-terminated polyether prepared in this example... 1 H NMR spectrum, GPC plot as follows Figure 1 , 2As shown, dielyl-terminated polyether 1 H NMR spectrum, GPC plot as follows Figure 3 , 4 As shown.

[0037] Example 2 In a glove box, POSS-B8 (2.5 μmol, 4 mg, 0.5 equivalents), TBASA (2.5 μmol, 1.5 mg, 0.5 equivalents), allyl alcohol (1.5 mmol, 100 μL, 300 equivalents), and PO (30 mmol, 2.1 mL, 6000 equivalents) were sequentially added to a pre-flame-dried 15 mL pressure-resistant bottle containing a magnetic magnet. The pressure-resistant bottle was sealed and removed from the glove box. The reaction time was controlled at 5 h, and the reaction temperature was 25 °C, yielding a monoallyl-terminated polyether. GPC analysis showed a number-average molecular weight (Mn) of 0.7 kg / mol, and a molecular weight distribution... The molecular weight was 1.07. After obtaining the monoallyl-terminated polyether, AGE (1.5 mmol, 178 μL, 300 equivalents) was added, and the reaction time was controlled at 3 h and the reaction temperature at 25 °C to obtain the dielyl-terminated polyether. The number-average molecular weight was measured by GPC. Mn It is 0.7 kg / mol, and the molecular weight distribution is... The value is 1.07. The monoallyl-terminated polyether prepared in this example... 1 H NMR spectrum, GPC plot as follows Figure 5 , 6 As shown, dielyl-terminated polyether 1 H NMR spectrum, GPC plot as follows Figure 7 , 8 As shown.

[0038] Example 3 In a glove box, POSS-B8 (5 μmol, 8 mg, 1 equivalent), TBASA (5 μmol, 3 mg, 1 equivalent), allyl alcohol (0.75 mmol, 50 μL, 150 equivalent), and PO (30 mmol, 2.1 mL, 6000 equivalent) were sequentially added to a pre-flame-dried 15 mL pressure-resistant bottle containing a magnetic magnet. The pressure-resistant bottle was sealed and removed from the glove box. The reaction time was controlled at 1.5 h, and the reaction temperature was 25 °C, yielding a monoallyl-terminated polyether. GPC analysis showed a number-average molecular weight (Mn) of 3.5 kg / mol, and a molecular weight distribution... The molecular weight was 1.04. After obtaining the monoallyl-terminated polyether, AGE (0.75 mmol, 89 μL, 150 equivalents) was added, and the reaction time was controlled at 2 h and the reaction temperature at 25 °C to obtain the dielyl-terminated polyether. The number-average molecular weight was measured by GPC. Mn It is 3.7 kg / mol, and the molecular weight distribution is... The value is 1.04. The monoallyl-terminated polyether prepared in this example... 1 H NMR spectrum, GPC plot as follows Figure 9 , 10 As shown, dielyl-terminated polyether 1 H NMR spectrum, GPC plot as follows Figure 11 , 12 As shown.

[0039] Example 4 In a glove box, POSS-B8 (5 μmol, 8 mg, 1 equivalent), TBACl (5 μmol, 1.4 mg, 1 equivalent), allyl alcohol (1.5 mmol, 100 μL, 300 equivalent), and PO (30 mmol, 2.1 mL, 6000 equivalent) were sequentially added to a pre-flame-dried 15 mL pressure-resistant bottle containing a magnetic magnet. The pressure-resistant bottle was sealed and removed from the glove box. The reaction time was controlled at 1.5 h, and the reaction temperature was 25 °C, yielding a monoallyl-terminated polyether. GPC analysis showed a number-average molecular weight (Mn) of 1.7 kg / mol, and a molecular weight distribution... The molecular weight was 1.06. After obtaining the monoallyl-terminated polyether, AGE (1.5 mmol, 178 μL, 300 equivalents) was added, and the reaction time was controlled at 2 h and the reaction temperature at 25 °C to obtain the dielyl-terminated polyether. The number-average molecular weight was measured by GPC. Mn It is 1.8 kg / mol, and the molecular weight distribution is... The value is 1.06. The monoallyl-terminated polyether prepared in this example... 1 H NMR spectrum, GPC plot as follows Figure 13 , 14 As shown, dielyl-terminated polyether 1 H NMR spectrum, GPC plot as follows Figure 15 , 16 As shown.

[0040] Example 5 In a glove box, POSS-B8 (5 μmol, 8 mg, 1 equivalent), potassium methoxide (5 μmol, 0.35 mg, 1 equivalent), allyl alcohol (1.5 mmol, 100 μL, 300 equivalent), and PO (30 mmol, 2.1 mL, 6000 equivalent) were sequentially added to a pre-flame-dried 15 mL pressure-resistant bottle containing a magnetic magnet. The pressure-resistant bottle was sealed and removed from the glove box. The reaction time was controlled at 18 h, and the reaction temperature was 25 °C, yielding a monoallyl-terminated polyether. GPC analysis showed a number-average molecular weight (Mn) of 1.5 kg / mol and a molecular weight distribution of... The molecular weight was 1.08. After obtaining the monoallyl-terminated polyether, AGE (1.5 mmol, 178 μL, 300 equivalents) was added, and the reaction time was controlled at 4 h and the reaction temperature at 25 °C to obtain the dielyl-terminated polyether. The number-average molecular weight was determined by GPC. Mn It is 1.6 kg / mol, and the molecular weight distribution is... The value is 1.07. The monoallyl-terminated polyether prepared in this example... 1 H NMR spectrum, GPC plot as follows Figure 17 , 18 As shown, dielyl-terminated polyether 1 H NMR spectrum, GPC plot as follows Figure 19 , 20 As shown.

[0041] Example 6 In a glove box, POSS-B8 (5 μmol, 8 mg, 1 equivalent), potassium tert-butoxide (5 μmol, 0.56 mg, 1 equivalent), allyl alcohol (1.5 mmol, 100 μL, 300 equivalent), and PO (30 mmol, 2.1 mL, 6000 equivalent) were sequentially added to a pre-flame-dried 15 mL pressure-resistant bottle containing a magnetic magnet. The pressure-resistant bottle was sealed and removed from the glove box. The reaction time was controlled at 18 h, and the reaction temperature was 25 °C, yielding a monoallyl-terminated polyether. GPC analysis showed a number-average molecular weight (Mn) of 1.5 kg / mol and a molecular weight distribution of... The molecular weight was 1.07. After obtaining the monoallyl-terminated polyether, AGE (1.5 mmol, 178 μL, 300 equivalents) was added, and the reaction time was controlled at 3 h and the reaction temperature at 25 °C to obtain the dielyl-terminated polyether. The number-average molecular weight was measured by GPC. Mn It is 1.6 kg / mol, and the molecular weight distribution is... The value is 1.07. The monoallyl-terminated polyether prepared in this example... 1 H NMR spectrum, GPC plot as follows Figure 21 , 22 As shown, dielyl-terminated polyether 1 H NMR spectrum, GPC plot as follows Figure 23 , 24 As shown.

[0042] Example 7 In a glove box, POSS-B8 (5 μmol, 8 mg, 1 equivalent), TBACl (5 μmol, 1.4 mg, 1 equivalent), allyl alcohol (0.75 mmol, 50 μL, 150 equivalent), and PO (30 mmol, 2.1 mL, 6000 equivalent) were sequentially added to a pre-flame-dried 15 mL pressure-resistant bottle containing a magnetic magnet. The pressure-resistant bottle was sealed and removed from the glove box. The reaction time was controlled at 5 h, and the reaction temperature was 25 °C, yielding a monoallyl-terminated polyether. GPC analysis showed a number-average molecular weight (Mn) of 3.5 kg / mol, and a molecular weight distribution... The molecular weight was 1.04. After obtaining the monoallyl-terminated polyether, AGE (0.75 mmol, 89 μL, 150 equivalents) was added, and the reaction time was controlled at 3 h and the reaction temperature at 25 °C to obtain the dielyl-terminated polyether. The number-average molecular weight was measured by GPC. Mn It is 3.6 kg / mol, and the molecular weight distribution is... The value is 1.04. The monoallyl-terminated polyether prepared in this example... 1 H NMR spectrum, GPC plot as follows Figure 25 , 26 As shown, dielyl-terminated polyether 1 H NMR spectrum, GPC plot as follows Figure 27 , 28 As shown.

[0043] Example 8 In a glove box, POSS-B8 (5 μmol, 8 mg, 1 equivalent), TBACl (5 μmol, 1.4 mg, 1 equivalent), allyl alcohol (0.225 mmol, 15.3 μL, 45 equivalent), and PO (31.05 mmol, 2.17 mL, 6210 equivalent) were added sequentially to a 15 mL pressure-resistant bottle pre-dried in a pre-flame-dried container equipped with a magnetic magnet. The pressure-resistant bottle was sealed and removed from the glove box. The reaction time was controlled at 5 h, and the reaction temperature was 25 °C, yielding a monoallyl-terminated polyether. GPC analysis showed a number-average molecular weight (Mn) of 10.1 kg / mol and a molecular weight distribution of... The molecular weight was 1.05. After obtaining the monoallyl-terminated polyether, AGE (0.225 mmol, 26.7 μL, 45 equivalents) was added, and the reaction time was controlled at 3 h and the reaction temperature at 25 °C to obtain the dielyl-terminated polyether. The number-average molecular weight was determined by GPC. Mn It is 10.3 kg / mol, and the molecular weight distribution is... The value is 1.05. The monoallyl-terminated polyether prepared in this example... 1 H NMR spectrum, GPC plot as follows Figure 29 , 30 As shown, dielyl-terminated polyether1 H NMR spectrum, GPC plot as follows Figure 31 , 32 As shown.

[0044] Example 9 In a glove box, POSS-B8 (5 μmol, 8 mg, 1 equivalent), TBACl (5 μmol, 1.4 mg, 1 equivalent), allyl alcohol (0.15 mmol, 10.2 μL, 30 equivalent), and PO (31.5 mmol, 2.2 mL, 6300 equivalent) were sequentially added to a pre-flame-dried 15 mL pressure-resistant bottle containing a magnetic magnet. The pressure-resistant bottle was sealed and removed from the glove box. The reaction time was controlled at 5 h, and the reaction temperature was 25 °C, yielding a monoallyl-terminated polyether. GPC analysis showed a number-average molecular weight (Mn) of 13.8 kg / mol and a molecular weight distribution of... The molecular weight was 1.07. After obtaining the monoallyl-terminated polyether, AGE (0.15 mmol, 17.8 μL, 30 equivalents) was added, and the reaction time was controlled at 3 h and the reaction temperature at 25 °C to obtain the diallyl-terminated polyether. The number-average molecular weight was measured by GPC. Mn It is 15.2 kg / mol, and the molecular weight distribution is... It is 1.07.

[0045] Example 10 In a glove box, POSS-B8 (5 μmol, 8 mg, 1 equivalent), TBACl (5 μmol, 1.4 mg, 1 equivalent), allyl alcohol (0.275 mmol, 18.8 μL, 55 equivalent), and PO (100 mmol, 7 mL, 20000 equivalent) were sequentially added to a pre-flame-dried 15 mL pressure-resistant bottle containing a magnetic magnet. The pressure-resistant bottle was sealed and removed from the glove box. The reaction time was controlled at 12 h and the reaction temperature at 25 °C, yielding a monoallyl-terminated polyether with a molecular weight of 21.1 kg / mol. After obtaining the monoallyl-terminated polyether, AGE (0.275 mmol, 32.6 μL, 55 equivalent) was added, and the reaction time was controlled at 3 h and the reaction temperature at 25 °C, yielding a dielyl-terminated polyether. The number-average molecular weight was measured by GPC. Mn It is 21.2 kg / mol, and the molecular weight distribution is... It is 1.07.

[0046] Example 11 In a glove box, cat 1-1 (5 μmol, 50 mg, 1 equivalent), TBACl (5 μmol, 1.4 mg, 1 equivalent), allyl alcohol (1.5 mmol, 100 μL, 300 equivalent), and PO (30 mmol, 2.1 mL, 6000 equivalent) were sequentially added to a pre-flame-dried 15 mL pressure-resistant bottle containing a magnetic magnet. The pressure-resistant bottle was sealed and removed from the glove box. The reaction time was controlled at 3 h, and the reaction temperature was 25 °C, yielding a monoallyl-terminated polyether. GPC analysis showed a number-average molecular weight (Mn) of 1.5 kg / mol, and a molecular weight distribution... The molecular weight was 1.05. After obtaining the monoallyl-terminated polyether, AGE (1.5 mmol, 178 μL, 300 equivalents) was added, and the reaction time was controlled at 2 h and the reaction temperature at 25 °C to obtain the dielyl-terminated polyether. The number-average molecular weight was determined by GPC. Mn It is 1.7 kg / mol, and the molecular weight distribution is... It is 1.05.

[0047] Example 12 In a glove box, cat 2-1 (5 μmol, 137 mg, 1 equivalent), TBACl (5 μmol, 93 mg, 1 equivalent), allyl alcohol (1.5 mmol, 100 μL, 300 equivalent), and PO (30 mmol, 2.1 mL, 6000 equivalent) were sequentially added to a pre-flame-dried 15 mL pressure-resistant bottle containing a magnetic magnet. The pressure-resistant bottle was sealed and removed from the glove box. The reaction time was controlled at 3 h, and the reaction temperature was 25 °C, yielding a monoallyl-terminated polyether. GPC analysis showed a number-average molecular weight (Mn) of 1.7 kg / mol, and a molecular weight distribution... The molecular weight was 1.07. After obtaining the monoallyl-terminated polyether, AGE (1.5 mmol, 178 μL, 300 equivalents) was added, and the reaction time was controlled at 2 h and the reaction temperature at 25 °C to obtain the dielyl-terminated polyether. The number-average molecular weight was measured by GPC. Mn It is 1.8 kg / mol, and the molecular weight distribution is... It is 1.06.

[0048] Example 13 In a glove box, V4B (5 μmol, 10 μL, 1 equivalent), TBASA (5 μmol, 3 mg, 1 equivalent), allyl alcohol (1.5 mmol, 100 μL, 300 equivalent), and PO (30 mmol, 2.1 mL, 6000 equivalent) were sequentially added to a pre-flame-dried 15 mL pressure-resistant bottle containing a magnetic magnet. The pressure-resistant bottle was sealed and removed from the glove box. The reaction time was controlled at 6 h, and the reaction temperature was 25 °C, yielding a monoallyl-terminated polyether. GPC analysis showed a number-average molecular weight (Mn) of 1.4 kg / mol, and a molecular weight distribution... The molecular weight was 1.05. After obtaining the monoallyl-terminated polyether, AGE (1.5 mmol, 178 μL, 300 equivalents) was added, and the reaction time was controlled at 2 h and the reaction temperature at 25 °C to obtain the dielyl-terminated polyether. The number-average molecular weight was determined by GPC. Mn It is 1.5 kg / mol, and the molecular weight distribution is... It is 1.06.

[0049] Example 14 In a glove box, POSS-B8 (5 μmol, 8 mg, 1 equivalent), TBACl (5 μmol, 1.4 mg, 1 equivalent), allyl alcohol (1.5 mmol, 100 μL, 300 equivalent), PO (30 mmol, 2.1 mL, 6000 equivalent), and EO (15 mmol, 803 μL, 3000 equivalent) were sequentially added to a pre-flame-dried 15 mL pressure-resistant bottle containing a magnetic magnet. The pressure-resistant bottle was sealed and removed from the glove box. The reaction time was controlled at 3 h, and the reaction temperature was 25 °C, yielding a monoallyl-terminated polyether. GPC analysis showed a number-average molecular weight (Mn) of 3.5 kg / mol, and a molecular weight distribution... The molecular weight was 1.08. After obtaining the monoallyl-terminated polyether, AGE (1.5 mmol, 178 μL, 300 equivalents) was added, and the reaction time was controlled at 2 h and the reaction temperature at 25 °C to obtain the dielyl-terminated polyether. The number-average molecular weight was determined by GPC. Mn It is 3.9 kg / mol, and the molecular weight distribution is... It is 1.07.

[0050] Key data from Examples 1-14 are summarized in Table 1.

[0051] Table 1 Summary of Key Data from Examples 1-14

[0052] After hydrosilylation, the polymer prepared by this method has two hydroxyl groups in its side chain, which allows for better cross-linking of the subsequent polymer, resulting in better adhesion of the prepared MS adhesive.

[0053]

[0054]

[0055] The above description is merely a preferred embodiment of the present invention and is not intended to limit the invention. Various modifications and variations can be made to the present invention by those skilled in the art. Any modifications, equivalent substitutions, improvements, etc., made within the spirit and principles of the present invention should be included within the scope of protection of the present invention.

Claims

1. A novel dielyl-terminated polyether, characterized in that, Its structure is shown in equations (I) and (II): 、 Formula (I) Formula (II) Where n is any positive integer from 20 to 210; m is any positive integer from 1 to 210.

2. The method for synthesizing diallyl-terminated polyether as described in claim 1, characterized in that, Includes the following steps: (1) The catalyst, initiator and epoxy monomer are added to the reaction apparatus in sequence, and the reaction is carried out for 1.5-18 h after sealing to obtain monoallyl-terminated polyether; the catalyst is a mixture of polynuclear organoboron Lewis acid and Lewis base to obtain an acid-base pair; (2) Add allyl glycidyl ether AGE to the generated monoallyl-terminated polyether, seal and react for 2-24 h to obtain dielyl-terminated polyether; The epoxy compound monomer is propylene oxide or a mixture of propylene oxide and ethylene oxide.

3. The synthesis method as described in claim 2, characterized in that, In step (1), the molar ratio of epoxy monomer, initiator, Lewis acid and Lewis base is (6000~20000):(30~300):1:1; or, when the epoxy monomer is PO and EO, the molar ratio of PO and EO is 1-10:1; preferably 1-6:1, more preferably 2:

1.

4. The synthesis method according to claim 2, characterized in that, In step (1), a magnetic stirrer is used to stir the reaction; or, in step (1), the reaction temperature is 20-25℃ and the reaction pressure is atmospheric pressure.

5. The synthesis method as described in claim 2, characterized in that, In step (1), the initiator is allyl alcohol or low molecular weight allyl-terminated polyoxypropylene. The number-average molecular weight is 100-500 g / mol.

6. The synthesis method according to claim 2, characterized in that, The polynuclear organoboron Lewis acid is: or or or ; Among them, BY2 is selected independently. , , , or ; R1 is independently selected from hydrogen, halogen, and optionally substituted straight-chain or branched C1-C8 alkyl, C1-C8 alkoxy, C1-C8 alkenyl, C1-C8 alkynyl, and optionally substituted aromatic, fused-ring aromatic or C3-C8 heterocyclic groups. The substituent is selected from halogens, C1-C... 10 Alkyl, halogenated C1-C 10 Alkyl, C1-C 10 The group may be alkoxy, hydroxy, cyano, nitro, amino, or aromatic; the heteroatom in the C3-C8 heterocyclic group may be selected from oxygen, sulfur, or nitrogen. x is any positive integer from 3 to 5000, y is any positive integer from 3 to 5000, h is any positive integer from 1 to 20, and z is any positive integer from 1 to 5; The Lewis base is: , Potassium tert-butoxide or potassium methoxide.

7. The synthesis method according to claim 6, characterized in that, The polynuclear organoboron Lewis acid is: , , or .

8. The synthesis method according to claim 2, characterized in that, In step (2), the molar ratio of AGE to initiator is 1:1-1.2; or, the reaction temperature is 20-25℃ and the reaction pressure is atmospheric pressure; or, the reaction time is 2-12 h; more preferably 2-6 h.

9. The synthesis method according to claim 2, characterized in that, In step (2), the molecular weight of the dielyl-terminated polyether is 0.6-22 kg / mol and the molecular weight distribution is ≤1.

10.

10. The application of the dielyl-terminated polyether as described in claim 1 in the fields of specialty electronic products, elastomers, and coatings.

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