CN104592473A - Preparation method of POSS modified polyurethane resin - Google Patents

Preparation method of POSS modified polyurethane resin Download PDF

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Publication number
CN104592473A
CN104592473A CN201310529272.6A CN201310529272A CN104592473A CN 104592473 A CN104592473 A CN 104592473A CN 201310529272 A CN201310529272 A CN 201310529272A CN 104592473 A CN104592473 A CN 104592473A
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poss
reaction
add
modified polyurethane
polyurethane resin
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沈连根
郦聪
张勇
徐欣欣
石磊
纪尚超
沈建峰
沈雁宾
李寿伟
息锁柱
赵磊
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JIAXING HEXIN CHEMICAL INDUSTRY CO LTD
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JIAXING HEXIN CHEMICAL INDUSTRY CO LTD
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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
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/08—Processes
    • C08G18/10—Prepolymer processes involving reaction of isocyanates or isothiocyanates with compounds having active hydrogen in a first reaction step
    • C08G18/12—Prepolymer processes involving reaction of isocyanates or isothiocyanates with compounds having active hydrogen in a first reaction step using two or more compounds having active hydrogen in the first polymerisation step
    • 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
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/40—High-molecular-weight compounds
    • C08G18/4009—Two or more macromolecular compounds not provided for in one single group of groups C08G18/42 - C08G18/64
    • 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
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/40—High-molecular-weight compounds
    • C08G18/42—Polycondensates having carboxylic or carbonic ester groups in the main chain
    • C08G18/4236—Polycondensates having carboxylic or carbonic ester groups in the main chain containing only aliphatic groups
    • C08G18/4238—Polycondensates having carboxylic or carbonic ester groups in the main chain containing only aliphatic groups derived from dicarboxylic acids and dialcohols
    • 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
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/40—High-molecular-weight compounds
    • C08G18/42—Polycondensates having carboxylic or carbonic ester groups in the main chain
    • C08G18/44—Polycarbonates
    • 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
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/40—High-molecular-weight compounds
    • C08G18/48—Polyethers
    • C08G18/4854—Polyethers containing oxyalkylene groups having four carbon atoms in the alkylene group
    • 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
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/40—High-molecular-weight compounds
    • C08G18/61—Polysiloxanes
    • 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
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/65—Low-molecular-weight compounds having active hydrogen with high-molecular-weight compounds having active hydrogen
    • C08G18/6505—Low-molecular-weight compounds having active hydrogen with high-molecular-weight compounds having active hydrogen the low-molecular compounds being compounds of group C08G18/32 or polyamines of C08G18/38
    • C08G18/6511—Low-molecular-weight compounds having active hydrogen with high-molecular-weight compounds having active hydrogen the low-molecular compounds being compounds of group C08G18/32 or polyamines of C08G18/38 compounds of group C08G18/3203
    • 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
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/65—Low-molecular-weight compounds having active hydrogen with high-molecular-weight compounds having active hydrogen
    • C08G18/66—Compounds of groups C08G18/42, C08G18/48, or C08G18/52
    • C08G18/6633—Compounds of group C08G18/42
    • C08G18/6637—Compounds of group C08G18/42 with compounds of group C08G18/32 or polyamines of C08G18/38
    • C08G18/664—Compounds of group C08G18/42 with compounds of group C08G18/32 or polyamines of C08G18/38 with compounds of group C08G18/3203

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  • Polymers & Plastics (AREA)
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  • Polyurethanes Or Polyureas (AREA)

Abstract

A preparation method of POSS (polyhedral oligomeric silsesquioxane) modified polyurethane resin comprises the following steps: preparing POSS diol by using trihydroxy cage-like siloxane heptamer, triethylamine, tetrahydrofuran, SiCl4, dimethylchlorosilane, tetrahydrophthalic anhydride, LiAlH4 and potassium sodium tartrate; and polymerizing the POSS diol, polyether diol, polyester diol and isocyanate to obtain the POSS modified polyurethane resin. The method allows the novel POSS modified polyurethane resin to be obtained by using the POSS diol, and can effectively overcome the compatibility problem existing in the modification of common inorganic substances; and the obtained POSS modified polyurethane resin has large tensile strength, impact strength, shearing strength and other mechanical performances, and also has the advantages of low surface energy, good heat resistance and good wear resistance.

Description

The preparation method of POSS modified polyurethane resin
Technical field
The present invention relates to a kind of preparation method of urethane resin, a kind of preparation method of POSS modified polyurethane resin.
Background technology
Urethane is the abbreviation of polyurethane(s), refer on macromolecular main chain containing repeating urethane unit, except containing except a large amount of ammonia ester bonds, the hydrogen bond etc. between ester bond, ehter bond, urea key, allophanic acid ester bond, isocyanurate-bond, macromole also may be contained.Urethane is with soft section of the flexibility of polyester or polyethers composition and the block polymer that is alternately formed by connecting with the hard section of the rigidity such as carbamate, urea groups; Because of thermodynamics uncompatibility that is soft, hard segment, soft section and hard section each self aggregation in the polymer, form soft section of phase and hard section phase, and microphase-separated occurs.Because urethane has unique micro phase separation structure, so have the performances such as excellent elasticity, wear resistance, shock resistance and stretching, coating, rubber, tamanori, fiber, flex foam, rigid foam, lagging material, synthetic leather, water-proof material, pavement material etc. are widely used in.But common polyurethane resin often also exists the problems such as wear resistance deficiency, poor heat resistance, and when adopting silicon-dioxide etc. inorganic nano particle modified, easily there is the problem of consistency, adopt the organic-silicon-modified crystallization that can destroy again between polyurethane molecular, affect its physical and mechanical properties.POSS molecule (Polyhedral Oligameric Silsesquioxanes, polyhedral oligomeric silsesquioxane) there is nanostructure inorganic framework core, peripheral to be surrounded by organic group, hybrid systems in the organic/inorganic molecule of POSS molecule inherently on a molecular level.This structure not only combines organic and inorganic component superiority separately, and can also produce new performance due to the synergistic effect of the two.For improving the performance of urethane resin and film, broadened application scope, needs to carry out POSS modification to it.
Summary of the invention
The present invention is intended to the preparation method proposing a kind of POSS modified polyurethane resin, the performance such as resistance to soiling, water tolerance, thermotolerance, wear resistance of the urethane resin obtained by raising.
The preparation method of this POSS modified polyurethane resin comprises the following steps:
(1) under nitrogen protection, add trihydroxy-seven successively and gather cage type siloxanes R 7si 8o 9(OH) 3, triethylamine and tetrahydrofuran (THF), then slowly inject SiCl 4after stirring is spent the night, cross and filter precipitation, filtrate rotary evaporation, obtain chlorination POSS(R 7si 8o 12cl), wherein R is i-C 4h 9, CH 3, C 6h 5in one;
(2) by chlorination POSS(R 7si 8o 12cl) reflux 72-90h in the mixing solutions of tetrahydrofuran (THF) and water, after rotary evaporation desolventizes, obtains hydroxylation POSS(R 7si 8o 12(OH));
(3) under nitrogen protection, hydroxylation POSS(R is added successively 7si 8o 12(OH)), tetrahydrofuran (THF), triethylamine, then slowly chlorodimethyl silane is added, 50-80 DEG C of reaction 15-20h, reaction product is transferred in separating funnel, use deionized water successively, after 5% hydrochloric acid soln and saturated NaCl solution are washed, filtrate is revolved and is steamed final vacuum drying, obtains alkylation POSS(R 7si 8o 12si (CH 3) 2h);
(4) under nitrogen protection, Pt catalyzer is joined alkylation POSS(R 7si 8o 12si (CH 3) 2h) and in the toluene solution of Tetra Hydro Phthalic Anhydride (THPA), 50-80 DEG C of reaction 40-70h, revolve steam desolventize after the solid that obtains add in normal hexane, backflow 30min, cooling, filters, remove excessive Tetra Hydro Phthalic Anhydride, filtrate is revolved the solid after steaming and add activated carbon backflow 3h in acetone, the remaining Pt catalyzer of absorption removing, centrifugal, supernatant layer is collected, and revolves steaming, obtain white solid, reflux 2h in diacetyl oxide, revolves and steam final vacuum drying, obtain acid anhydrides POSS(R 7si 8o 12si (CH 3) 2tHPA);
(5) by LiAlH 4tetrahydrofuran solution be slowly added drop-wise to acid anhydrides POSS(R 7si 8o 12si (CH 3) 2tHPA), in tetrahydrofuran solution, reflux stir 1-3h at-10-10 DEG C after 10-20h; In reaction system, add soluble tartrate saturated aqueous solution of sodium until bubble-free effusion, continue backflow 10-20h, filter, by washed with diethylether precipitation, merge tetrahydrofuran (THF) and diethyl ether solution, anhydrous sodium sulfate drying, boils off solvent, obtains POSS dibasic alcohol;
(6) polyether Glycols, polyester diol and appropriate isocyanic ester are heated in a solvent carry out prepolymerization reaction;
(7) in the performed polymer that (6) step is obtained, add the obtained POSS dibasic alcohol of solvent, (5) step and chainextender, continue heating and make it react;
(8) in upper step reactant, add poly-dihydric alcohol continue reaction, and add solvent in reaction process, detecting the viscosity of resin, as reached default viscosity number, then adding solvent, terminator, terminate reaction; If do not reach default viscosity number, then add chainextender continue reaction, until add solvent when reaching default viscosity number, terminator terminate reaction.
Method of the present invention is owing to applying POSS dibasic alcohol, obtain novel POSS modified polyurethane resin, thus there is following characteristics: (1) POSS dibasic alcohol be on molecular level organic/non-polar molecule in hybrid systems, effectively can overcome the compatibility problem of common mineral-modified middle existence; (2) the POSS modified polyurethane resin prepared has better mechanical property, as large in tensile strength, shock strength is large, shearing resistance is large; (3) the POSS modified polyurethane resin application performance prepared is better, has the advantages such as surface energy is low, good heat resistance, wear resistance are good.
Embodiment
The preparation method of this POSS modified polyurethane resin comprises the following steps:
(1) under nitrogen protection, add trihydroxy-seven successively and gather cage type siloxanes (R 7si 7o 9(OH) 3), triethylamine and tetrahydrofuran (THF), then slowly inject SiCl 4after stirring is spent the night, cross and filter Et 3nHCl, filtrate rotary evaporation, obtains compound 1 chlorination POSS((i-C 4h 9) 7si 7o 12cl).Its reaction formula is as follows:
In formula, R is i-C 4h 9, CH 3, C 6h 5
(2) by compound 1(R 7si 8o 12cl) at THF/H 2reflux in O mixing solutions 72-90h, after rotary evaporation desolventizes, obtains compound 2 hydroxylation POSS(R 7si 8o 12(OH)).Its reaction formula is as follows:
(3) compound 2 hydroxylation POSS(R under nitrogen protection, is added successively 7si 8o 12(OH)), tetrahydrofuran (THF), triethylamine, then slowly adds chlorodimethyl silane, can see the precipitation producing white, and 50-80 DEG C of reaction 15-20h, is transferred to reaction product in separating funnel.Also be transferred in separating funnel by solution after anhydrous diethyl ether cleaning reaction flask, use deionized water successively, after 5% hydrochloric acid soln and saturated NaCl solution are washed, filtrate obtains compound after revolving steaming, vacuum-drying 12h, obtains compound 3 alkylation POSS(R 7si 8o 12si (CH 3) 2h).Its reaction formula is as follows:
(4) under nitrogen protection, Pt catalyzer is joined compound 3 alkylation POSS(R 7si 8o 12si (CH 3) 2h) and in the toluene solution of Tetra Hydro Phthalic Anhydride (THPA), 50-80 DEG C of reaction 40-70h, revolving the solid obtained after steaming desolventizes adds in normal hexane, backflow 30min, cooling, filters, removes excessive Tetra Hydro Phthalic Anhydride, filtrate is revolved the solid after steaming and add activated carbon backflow 3h in acetone, the remaining Pt catalyzer of absorption removing, centrifugal, supernatant layer is collected, revolve steaming, obtain white solid, reflux 2h in diacetyl oxide, obtains compound after revolving steaming, vacuum-drying 12h, obtains compound 4 acid anhydrides POSS(R 7si 8o 12si (CH 3) 2tHPA).Its reaction formula is as follows:
(5) by LiAlH 4tetrahydrofuran solution be slowly added drop-wise in the tetrahydrofuran solution of acid anhydrides POSS, reflux stir 1-3h at-10-10 DEG C after 10-20h.In reaction system, add soluble tartrate saturated aqueous solution of sodium until bubble-free effusion, continue backflow 10-20h, filter, by washed with diethylether precipitation, merge tetrahydrofuran (THF) and diethyl ether solution, anhydrous sodium sulfate drying, filter, boil off solvent, obtain compound 5POSS dibasic alcohol.Its reaction formula is as follows
(6) polyether Glycols, polyester diol and appropriate isocyanic ester are heated in a solvent carry out prepolymerization reaction.
(7) in the performed polymer that (6) step is obtained, add the obtained POSS dibasic alcohol of solvent, (5) step and chainextender, continue heating and itself and above-mentioned prepolymer are reacted.
(8) continue to add poly-dihydric alcohol, chainextender and above-mentioned reactant reaction, and add solvent in reaction process, detecting the viscosity of resin, as reached default viscosity number, then adding solvent, terminator, terminate reaction; If do not reach default viscosity number, then add chainextender continue reaction, until add solvent when reaching default viscosity number, terminator terminate reaction.
In the preparation method of this POSS modified polyurethane resin, the described trihydroxy-seven in (1) step gathers that cage type siloxanes can be that trihydroxy-seven isobutyl-seven gathers cage type siloxanes, trihydroxy-seven methyl seven gathers cage type siloxanes, trihydroxy-seven phenyl seven gathers one in cage type siloxanes; R 7si 8o 9(OH) 3with SiCl 4mol ratio can be 1: (1 ~ 1.5).
In the preparation method of this POSS modified polyurethane resin, the described compound 2R in (3) step 7si 8o 12(OH) can be 1 with the mol ratio of chlorodimethyl silane: (1 ~ 1.3).
In the preparation method of this POSS modified polyurethane resin, the described compound 3R in (4) step 7si 8o 12si (CH 3) 2the mol ratio of H and Tetra Hydro Phthalic Anhydride can be 1: (1 ~ 1.1).
In the preparation method of this POSS modified polyurethane resin, described compound 4 acid anhydrides POSS and the LiAlH in (5) step 4mol ratio can be 1: (2 ~ 4).
In the preparation method of this POSS modified polyurethane resin, described isocyanic ester in (6) step can be 4, one or more in 4 '-diphenylmethanediisocyanate, tolylene diisocyanate, isophorone diisocyanate, hydrogenated diphenyl methane diisocyanate or 1,6-hexamethylene diisocyanate; Described polyether Glycols can be one or more in polyoxyethylene glycol, polyoxypropyleneglycol, PTMG, and molecular weight is 1000 ~ 4000; Described polyester polyol can be polyethylene glycol adipate glycol, and gather one or more in hexanodioic acid-BDO esterdiol, polyhexamethylene adipate glycol or polycarbonate diol, molecular weight is 1000 ~ 4000; Described isocyanic ester and the mol ratio of poly-dihydric alcohol are (1.2 ~ 2): 1, and temperature of reaction is 60-100 DEG C.
In the preparation method of this POSS modified polyurethane resin, the described solvent in (6) described step comprise dimethyl formamide, butanone, toluene, ethyl acetate one or more.
In the preparation method of this POSS modified polyurethane resin, the described chainextender described in (7) step is ethylene glycol, BDO, 1,6-hexylene glycol, glycol ether, neopentyl glycol and 2-methyl isophthalic acid, one or more in ammediol; Described POSS dibasic alcohol and the weight ratio of performed polymer can be: (1 ~ 8): 100, and the weight ratio of chainextender and performed polymer is (3 ~ 20): 100, and temperature of reaction is 40 ~ 70 DEG C.
One or more in the preparation method of this POSS modified polyurethane resin, in the single methanol that the terminator described in described (8) step is methyl alcohol, ethanol, n-Butyl Amine 99 equimolecular quantity are less than 500g/mol, monoamine.
Embodiment 1
(1) under nitrogen protection, add trihydroxy-seven isobutyl-seven successively and gather cage type siloxanes (i-C 4h 9) 7si 8o 9(OH) 3(97g, 100mmol), triethylamine (30.3g, 100mmol) and tetrahydrofuran (THF) (250ml), then slowly inject SiCl 4(17g, 100mmol) crosses and filters precipitation, filtrate rotary evaporation, obtain 73g compound 1 chlorination POSS((i-C after stirring and spending the night 4h 9) 7si 8o 12cl).
(2) by 73g compound 1 chlorination POSS((i-C 4h 9) 7si 8o 12cl) reflux 78h in the mixing solutions of tetrahydrofuran (THF) (100ml) and water (200ml), after rotary evaporation desolventizes, obtains 68g compound 2 hydroxylation POSS((i-C 4h 9) 7si 8o 12(OH)).
(3) compound 2 hydroxylation POSS((i-C under nitrogen protection, is added successively 4h 9) 7si 8o 12(OH)) (65g, 78mmol), tetrahydrofuran (THF) (250ml), triethylamine (23g, 230mmol), then slowly adds chlorodimethyl silane (7.38g, 78mmol), can see the precipitation producing white, 50-80 DEG C of reaction 15-20h.Reaction product is transferred in separating funnel, with the solution after anhydrous diethyl ether cleaning reaction flask, also be transferred in separating funnel, use deionized water successively, after 5% hydrochloric acid soln and saturated NaCl solution are washed, filtrate obtains compound vacuum-drying 12h after revolving steaming, obtain 67.8g compound 3 alkylation POSS((i-C 4h 9) 7si 8o 12si (CH 3) 2h).
(4) under nitrogen protection, Pt catalyzer (0.01g) is joined alkylation POSS((i-C 4h 9) 7si 8o 12si (CH 3) 2h) (67.8g, 75.8mmol) with Tetra Hydro Phthalic Anhydride (THPA) (11.56g, in toluene (200ml) solution 76mmol), 60 DEG C of reaction 60h, revolving the solid obtained after steaming desolventizes adds in normal hexane, backflow 30min, cooling, filter, remove excessive Tetra Hydro Phthalic Anhydride, filtrate is revolved the solid after steaming and add activated carbon backflow 3h in acetone, the remaining Pt catalyzer of absorption removing, centrifugal, supernatant layer is collected, revolve steaming, obtain white solid, reflux 2h in diacetyl oxide, compound is obtained after revolving steaming, vacuum-drying 12h, obtain 75g compound 4 acid anhydrides POSS((i-C 4h 9) 7si 8o 12si (CH 3) 2tHPA).
(5) by LiAlH 4the tetrahydrofuran solution (100ml) of (8.2g, 185mmol) is slowly added drop-wise to compound 4 acid anhydrides POSS((i-C 4h 9) 7si 8o 12si (CH 3) 2in the tetrahydrofuran solution (250ml) of THPA) (75g, 73mmol), reflux stir 2h at 0 DEG C after 15h.In reaction system, add soluble tartrate saturated aqueous solution of sodium (100g) until bubble-free effusion, continue backflow 15h, filter, by washed with diethylether precipitation, merge tetrahydrofuran (THF) and diethyl ether solution, anhydrous sodium sulfate drying, boils off solvent, obtains 65g POSS dibasic alcohol.
(6) add poly-hexanodioic acid-BDO esterdiol (molecular weight is 1000) 100g, DMF50g in the reactor, be heated to 45 DEG C and stir 25min; Add TDI20.9g, still temperature control was 75 DEG C of reactions 2 hours.
(7) add DMF150g, POSS dibasic alcohol 12.2g, control temperature of reaction 75 DEG C, detect and reach 1.0 × 10 to reacting viscosity 5mPas/25 DEG C.
(8), after adding DMF100g and chainextender EG6g stirring 30min, add MDI24.2g and continue reaction, temperature controls at 75 DEG C, reacts 1 hour; Drop into catalyzer (bismuth catalyst 0.1g), add DMF350g and continue reaction, then detect viscosity, until viscosity reaches 2.4 × 10 5mPas/25 DEG C; Add terminator methyl alcohol 0.06g and react 30min, discharging, obtains the urethane resin 816g that solid content is 20%.
Embodiment 2
(1) under nitrogen protection, add trihydroxy-seven isobutyl-seven successively and gather cage type siloxanes (i-C 4h 9) 7si 8o 9(OH) 3(79g, 100mmol), triethylamine (33.3g, 110mmol) and tetrahydrofuran (THF) (250ml), then slowly inject SiCl 4(20.4g, 120mmol) crosses and filters precipitation, filtrate rotary evaporation, obtain 78g compound 1 chlorination POSS((i-C after stirring and spending the night 4h 9) 7si 8o 12cl).
(2) by 78g compound 1 chlorination POSS((i-C 4h 9) 7si 8o 12cl) reflux 90h in the mixing solutions of tetrahydrofuran (THF) (100ml) and water (200ml), after rotary evaporation desolventizes, obtains 74g compound 2 hydroxylation POSS((i-C 4h 9) 7si 8o 12(OH)).
(3) compound 2 hydroxylation POSS((i-C under nitrogen protection, is added successively 4h 9) 7si 8o 12(OH)) (65g, 78mmol), tetrahydrofuran (THF) (250ml), triethylamine (23g, 230mmol), then slowly adds chlorodimethyl silane (8.86g, 93.6mmol), can see the precipitation 80 DEG C reaction 15h producing white.Reaction product is transferred in separating funnel, with the solution after anhydrous diethyl ether cleaning reaction flask, also be transferred in separating funnel, use deionized water successively, after 5% hydrochloric acid soln and saturated NaCl solution are washed, filtrate obtains compound vacuum-drying 12h after revolving steaming, obtain 68.5g compound 3 alkylation POSS((i-C 4h 9) 7si 8o 12si (CH 3) 2h).
(4) under nitrogen protection, Pt catalyzer (0.01g) is joined compound 3 alkylation POSS((i-C 4h 9) 7si 8o 12si (CH 3) 2h) (67.8g, 75.8mmol) with Tetra Hydro Phthalic Anhydride (THPA) (12.1g, in toluene (200ml) solution 80mmol), 70 DEG C of reaction 80h, revolving the solid obtained after steaming desolventizes adds in normal hexane, backflow 30min, cooling, filter, remove excessive Tetra Hydro Phthalic Anhydride, filtrate is revolved the solid after steaming and add activated carbon backflow 3h in acetone, the remaining Pt catalyzer of absorption removing, centrifugal, supernatant layer is collected, revolve steaming, obtain white solid, reflux 2h in diacetyl oxide, compound is obtained after revolving steaming, vacuum-drying 12h, obtain 75g compound 4 acid anhydrides POSS((i-C 4h 9) 7si 8o 12si (CH 3) 2tHPA).
(5) by LiAlH 4the tetrahydrofuran solution (100ml) of (12.8g, 290mmol) is slowly added drop-wise to compound 4 acid anhydrides POSS((i-C 4h 9) 7si 8o 12si (CH 3) 2in tetrahydrofuran (THF) (250ml) solution of THPA) (75g, 73mmol), reflux stir 3h at-5 DEG C after 15h.In reaction system, add soluble tartrate saturated aqueous solution of sodium (100g) until bubble-free effusion, continue backflow 20h, filter, by washed with diethylether precipitation, merge tetrahydrofuran (THF) and diethyl ether solution, anhydrous sodium sulfate drying, boils off solvent, obtains 68g POSS dibasic alcohol.
(6) drop into PCDL (molecular weight is 2000) 100g, DMF120g in the reactor, be heated to 45 DEG C, and stir 25min; Drop into MDI16.25g, still temperature control is at 80 DEG C of reaction 1.5h.
(7) add DMF150g, POSS dibasic alcohol 8g, control temperature of reaction 80 DEG C reaction 1 hour, add DMF50g and PTMG15g, be heated to still temperature 75 DEG C and continue reaction, detection reaches 1.5 × 10 to reaction viscosity 5mPas/25 DEG C.
(8), after adding chainextender Isosorbide-5-Nitrae-BG10g and DMF50g stirring 30min, add MDI20g, continue reaction, temperature controls at 75 DEG C, reacts 1 hour; Drop into catalyzer (bismuth catalyst 0.01g) reaction, add MEK137g and continue reaction, then detect viscosity, until viscosity reaches 2.5 × 10 5mPas/25 DEG C; Add methyl alcohol 0.14g and react 40min, discharging, obtains the urethane resin 677g that solid content is 25%.
Embodiment 3
(1) under nitrogen protection, add trihydroxy-seven phenyl seven successively and gather cage type siloxanes (C 6h 5) 7si 8o 9(OH) 3(93g, 100mmol), triethylamine (31.8g, 105mmol) and tetrahydrofuran (THF) (250ml), then slowly inject SiCl 4(18.7g, 110mmol) crosses and filters precipitation, filtrate rotary evaporation, obtain 95g compound 1 chlorination POSS((C after stirring and spending the night 6h 5) 7si 8o 12cl).
(2) by compound 1 chlorination POSS((C 6h 5) 7si 8o 12cl) (95g, 96mmol) refluxes 78h in the mixing solutions of tetrahydrofuran (THF) (100ml) and water (200ml), after rotary evaporation desolventizes, obtains compound 2 hydroxylation POSS((C 6h 5) 7si 8o 12(OH)) (91.5g, 94mmol).
(3) compound 2 hydroxylation POSS((C under nitrogen protection, is added successively 6h 5) 7si 8o 12(OH)) (77.8g, 80mmol), tetrahydrofuran (THF) (250ml), triethylamine (23g, 230mmol), then slowly adds chlorodimethyl silane (79.5g, 85mmol), can see the precipitation producing white.70 DEG C of reaction 18h.Reaction product is transferred in separating funnel, with the solution after anhydrous diethyl ether cleaning reaction flask, also be transferred in separating funnel, use deionized water successively, after 5% hydrochloric acid soln and saturated NaCl solution are washed, filtrate obtains compound vacuum-drying 12h after revolving steaming, obtain 78g compound 3 alkylation POSS((C 6h 5) 7si 8o 12si (CH 3) 2h).
(4) under nitrogen protection, Pt catalyzer (0.01g) is joined compound 3 alkylation POSS((C 6h 5) 7si 8o 12si (CH 3) 2h) (78g, 75.8mmol) with Tetra Hydro Phthalic Anhydride (THPA) (12.72g, in toluene (200ml) solution 83mmol), 70 DEG C of reaction 60h, revolving the solid obtained after steaming desolventizes adds in normal hexane, backflow 30min, cooling, filter, remove excessive Tetra Hydro Phthalic Anhydride, filtrate is revolved the solid after steaming and add activated carbon backflow 3h in acetone, the remaining Pt catalyzer of absorption removing, centrifugal, supernatant layer is collected, revolve steaming, obtain white solid, reflux 2h in diacetyl oxide, compound is obtained after revolving steaming, vacuum-drying 12h, obtain 75g compound 4 acid anhydrides POSS((C 6h 5) 7si 8o 12si (CH 3) 2tHPA).
(5) by LiAlH 4tetrahydrofuran (THF) (100ml) solution of (11.3g, 250mmol) is slowly added drop-wise to compound 4 acid anhydrides POSS((C 6h 5) 7si 8o 12si (CH 3) 2in tetrahydrofuran (THF) (200ml) solution of THPA) (75g, 64mmol), reflux stir 2h at-5 DEG C after 15h.In reaction system, add soluble tartrate saturated aqueous solution of sodium (100g) until bubble-free effusion, continue backflow 15h, filter, by washed with diethylether precipitation, merge tetrahydrofuran (THF) and diethyl ether solution, anhydrous sodium sulfate drying, boils off solvent, obtains POSS dibasic alcohol 72g.
(6) drop into PCDL (molecular weight is 1000) 50g, poly-hexanodioic acid-BDO esterdiol (molecular weight is 2000) 50g, DMF100g in the reactor, be heated to 45 DEG C, and stir 25min; Drop into MDI27.75g, still temperature control is at 80 DEG C of reaction 1.0h.
(7) DMF150g, POSS dibasic alcohol 17.2g is added, control temperature of reaction 50 DEG C reaction 1 hour, add DMF50g and poly-hexanodioic acid-BDO esterdiol (molecular weight is 1000) 22.2g, be heated to still temperature 75 DEG C and continue reaction, detect and reach 5.0 × 10 to reacting viscosity 4mPas/25 DEG C.
(8) add chainextender Isosorbide-5-Nitrae-BG7g, 1,2-PD 3g and 50g DMF, after stirring 30min, add MDI29.57g and continue reaction, temperature controls at 75 DEG C, reacts 1 hour; Drop into catalyzer (bismuth catalyst 0.1g) reaction, add DMF130g and continue reaction, then detect viscosity, until viscosity reaches 1.5 × 10 5mPas/25 DEG C; Add methyl alcohol 0.14g and react 40min, discharging, obtains the urethane resin 690g that solid content is 30%.
Embodiment 4
(1) under nitrogen protection, add trihydroxy-seven phenyl seven successively and gather cage type siloxanes (C 6h 5) 7si 8o 9(OH) 3(93g, 100mmol), triethylamine (31.8g, 105mmol) and tetrahydrofuran (THF) (250ml), then slowly inject SiCl 4(20.4g, 120mmol) crosses and filters precipitation, filtrate rotary evaporation, obtain 97.5g compound 1 chlorination POSS((C after stirring and spending the night 6h 5) 7si 8o 12cl).
(2) by compound 1 chlorination POSS((C 6h 5) 7si 8o 12cl) (97.5g, 100mmol) refluxes 78h in the mixing solutions of tetrahydrofuran (THF) (100ml) and water (200ml), after rotary evaporation desolventizes, obtains compound 2 hydroxylation POSS((C 6h 5) 7si 8o 12(OH)) (94.2g, 97mmol).
(3) compound 2 hydroxylation POSS((C under nitrogen protection, is added successively 6h 5) 7si 8o 12(OH)) (77.8g, 80mmol), tetrahydrofuran (THF) (200ml), triethylamine (23g, 230mmol), then slowly adds chlorodimethyl silane (79.5g, 85mmol), can see the precipitation producing white, 70 DEG C of reaction 18h.Reaction product is transferred in separating funnel, with the solution after anhydrous diethyl ether cleaning reaction flask, also be transferred in separating funnel, use deionized water successively, after 5% hydrochloric acid soln and saturated NaCl solution are washed, filtrate obtains compound vacuum-drying 12h after revolving steaming, obtain 78g compound 3 alkylation POSS((C 6h 5) 7si 8o 12si (CH 3) 2h).
(4) under nitrogen protection, Pt catalyzer (0.01g) is joined compound 3 alkylation POSS((C 6h 5) 7si 8o 12si (CH 3) 2h) (78g, 75.8mmol) with Tetra Hydro Phthalic Anhydride (THPA) (11.64g, in toluene (200ml) solution 76mmol), 70 DEG C of reaction 60h, revolving the solid obtained after steaming desolventizes adds in normal hexane, backflow 30min, cooling, filter, remove excessive Tetra Hydro Phthalic Anhydride, filtrate is revolved the solid after steaming and add activated carbon backflow 3h in acetone, the remaining Pt catalyzer of absorption removing, centrifugal, supernatant layer is collected, revolve steaming, obtain white solid, reflux 2h in diacetyl oxide, compound is obtained after revolving steaming, vacuum-drying 12h, obtain 73g compound 4 acid anhydrides POSS((C 6h 5) 7si 8o 12si (CH 3) 2tHPA).
(5) by LiAlH 4tetrahydrofuran (THF) (100ml) solution of (8.2g, 185mmol) is slowly added drop-wise to compound 4 acid anhydrides POSS((C 6h 5) 7si 8o 12si (CH 3) 2in tetrahydrofuran (THF) (200ml) solution of THPA) (73g, 62mmol), reflux stir 2h at-5 DEG C after 15h.In reaction system, add soluble tartrate saturated aqueous solution of sodium (100g) until bubble-free effusion, continue backflow 15h, filter, by washed with diethylether precipitation, merge tetrahydrofuran (THF) and diethyl ether solution, anhydrous sodium sulfate drying, boils off solvent, obtains POSS dibasic alcohol 70g.
(6) add PCDL (molecular weight is 2000) 50g, PTMG (molecular weight is 1000, and Japan produces) 80g, DMF100g in the reactor, be heated to 45 DEG C, and stir 25min; Drop into MDI49.55g, still temperature control is at 80 DEG C of reaction 1.0h.
(7) DMF150g, POSS dibasic alcohol 9g is added, control temperature of reaction 50 DEG C reaction 1 hour, add DMF50g and polytetrahydrofuran diol (molecular weight is 2000) 50g, be heated to still temperature 75 DEG C and continue reaction 1 hour, add DMF137g and continue reaction, detect viscosity again, until viscosity reaches 1.0 × 10 4mPas/25 DEG C; Add methyl alcohol 0.14g and react 40min, discharging, obtains the urethane resin 673g that solid content is 35%.
Embodiment 5
(1) under nitrogen protection, add trihydroxy-seven methyl seven successively and gather cage type siloxanes (CH 3) 7si 8o 9(OH) 3(50g, 100mmol), triethylamine (30.3g, 100mmol) and tetrahydrofuran (THF) (250ml), then slowly inject SiCl 4(17g, 100mmol) crosses and filters precipitation, filtrate rotary evaporation, obtain 52g compound 1 chlorination POSS((CH after stirring and spending the night 3) 7si 8o 12cl).
(2) by 52g compound 1 chlorination POSS((CH 3) 7si 8o 12cl) (52g, 94mmol) refluxes 78h in the mixing solutions of tetrahydrofuran (THF) (100ml) and water (200ml), after rotary evaporation desolventizes, obtains 49g compound 2 hydroxylation POSS((CH 3) 7si 8o 12(OH)).
(3) compound 2 hydroxylation POSS((CH under nitrogen protection, is added successively 3) 7si 8o 12(OH)) (49g, 92mmol), tetrahydrofuran (THF) (200ml), triethylamine (22.5g, 225mmol), then slowly adds chlorodimethyl silane (9g, 96mmol), can see the precipitation producing white, 50-80 DEG C of reaction 15-20h.Reaction product is transferred in separating funnel, with the solution after anhydrous diethyl ether cleaning reaction flask, also be transferred in separating funnel, use deionized water successively, after 5% hydrochloric acid soln and saturated NaCl solution are washed, filtrate obtains compound vacuum-drying 12h after revolving steaming, obtain 53.8g compound 3 alkylation POSS((CH 3) 7si 8o 12si (CH 3) 2h).
(4) under nitrogen protection, Pt catalyzer (0.01g) is joined compound 3 alkylation POSS((CH 3) 7si 8o 12si (CH 3) 2h) (53.8g, 90mmol) with Tetra Hydro Phthalic Anhydride (THPA) (15.2g, in toluene (200ml) solution 100mmol), 60 DEG C of reaction 60h, revolving the solid obtained after steaming desolventizes adds in normal hexane, backflow 30min, cooling, filter, remove excessive Tetra Hydro Phthalic Anhydride, filtrate is revolved the solid after steaming and add activated carbon backflow 3h in acetone, the remaining Pt catalyzer of absorption removing, centrifugal, supernatant layer is collected, revolve steaming, obtain white solid, reflux 2h in diacetyl oxide, compound is obtained after revolving steaming, vacuum-drying 12h, obtain 64g compound 4 acid anhydrides POSS((CH 3) 7si 8o 12si (CH 3) 2tHPA).
(5) by LiAlH 4the tetrahydrofuran solution (100ml) of (14g, 320mmol) is slowly added drop-wise to compound 4 acid anhydrides POSS((CH 3) 7si 8o 12si (CH 3) 2in tetrahydrofuran (THF) (200ml) solution of THPA) (64g, 85mmol), reflux stir 2h at 0 DEG C after 15h.In reaction system, add soluble tartrate saturated aqueous solution of sodium (100g) until bubble-free effusion, continue backflow 15h, filter, by washed with diethylether precipitation, merge tetrahydrofuran (THF) and diethyl ether solution, anhydrous sodium sulfate drying, boils off solvent, obtains 60g POSS dibasic alcohol.
(6) drop into PTMG (molecular weight is 1000) 50g, polyhexamethylene adipate glycol (molecular weight is 4000) 50g, DMF100g in the reactor, be heated to 45 DEG C, and stir 25min; Drop into MDI26.56g, still temperature control is at 80 DEG C of reaction 1.0h.
(7) add DMF100g, POSS dibasic alcohol 25g, control temperature of reaction 50 DEG C reaction 1 hour, add DMF50g and PCDL (molecular weight is 2000) 15g, be heated to still temperature 75 DEG C and continue reaction, detection reaches 1.5 × 10 to reaction viscosity 5mPas/25 DEG C.
(8) add chainextender 1,2-PD 8.4g, after DMF50g stirs 30min, add MDI25.24g and continue reaction, temperature controls at 75 DEG C, reacts 1 hour; Drop into catalyzer (bismuth catalyst 0.1g) reaction, add DMF120g and continue reaction, then detect viscosity, until viscosity reaches 1.5 × 10 5mPas/25 DEG C; Add methyl alcohol 0.14g and react 40min, discharging, obtains the urethane resin 572g that solid content is 35%.
Embodiment 6
(1) under nitrogen protection, add trihydroxy-seven methyl seven successively and gather cage type siloxanes (CH 3) 7si 8o 9(OH) 3(50g, 100mmol), triethylamine (30.3g, 100mmol) and tetrahydrofuran (THF) (250ml), then slowly inject SiCl 4(17g, 100mmol) crosses and filters precipitation, filtrate rotary evaporation, obtain 52g compound 1 chlorination POSS((CH after stirring and spending the night 3) 7si 8o 12cl).
(2) by compound 1 chlorination POSS((CH 3) 7si 8o 12cl) (52g, 94mmol) refluxes 78h in the mixing solutions of tetrahydrofuran (THF) (100ml) and water (200ml), after rotary evaporation desolventizes, obtains 49g compound 2 hydroxylation POSS((CH 3) 7si 8o 12(OH)).
(3) compound 2 hydroxylation POSS((CH under nitrogen protection, is added successively 3) 7si 8o 12(OH)) (49g, 92mmol), tetrahydrofuran (THF) (200ml), triethylamine (22.5g, 225mmol), then slowly adds chlorodimethyl silane (9g, 96mmol), can see the precipitation producing white, 50-80 DEG C of reaction 20h.Reaction product is transferred in separating funnel, with the solution after anhydrous diethyl ether cleaning reaction flask, also be transferred in separating funnel, use deionized water successively, after 5% hydrochloric acid soln and saturated NaCl solution are washed, filtrate obtains compound vacuum-drying 12h after revolving steaming, obtain 53.8g compound 3 alkylation POSS((CH 3) 7si 8o 12si (CH 3) 2h).
(4) under nitrogen protection, Pt catalyzer (0.01g) is joined compound 3 alkylation POSS((CH 3) 7si 8o 12si (CH 3) 2h) (53.8g, 90mmol) with Tetra Hydro Phthalic Anhydride (THPA) (15.2g, in toluene (200ml) solution 100mmol), 60 DEG C of reaction 60h, revolving the solid obtained after steaming desolventizes adds in normal hexane, backflow 30min, cooling, filter, remove excessive Tetra Hydro Phthalic Anhydride, filtrate is revolved the solid after steaming and add activated carbon backflow 3h in acetone, the remaining Pt catalyzer of absorption removing, centrifugal, supernatant layer is collected, revolve steaming, obtain white solid, reflux 2h in diacetyl oxide, compound is obtained after revolving steaming, vacuum-drying 12h, obtain 64g compound 4 acid anhydrides POSS((CH 3) 7si 8o 12si (CH 3) 2tHPA).
(5) by LiAlH 4tetrahydrofuran (THF) (100ml) solution of (14g, 320mmol) is slowly added drop-wise to compound 4 acid anhydrides POSS((CH 3) 7si 8o 12si (CH 3) 2in tetrahydrofuran (THF) (200ml) solution of THPA) (64g, 85mmol), reflux stir 2h at 0 DEG C after 15h.In reaction system, add soluble tartrate saturated aqueous solution of sodium (100g) until bubble-free effusion, continue backflow 15h, filter, by washed with diethylether precipitation, merge tetrahydrofuran (THF) and diethyl ether solution, anhydrous sodium sulfate drying, boils off solvent, obtains 60g POSS dibasic alcohol.
(6) PTMG (molecular weight is 3000) 30g, polyhexamethylene adipate glycol (molecular weight is 2000) 40g, PCDL (molecular weight is 2000) 30g, DMF50g is dropped in the reactor, be heated to 45 DEG C, and stir 25min; Drop into MDI47.25g, still temperature control is at 80 DEG C of reaction 1.0h.
(7) DMF100g, POSS dibasic alcohol 25g is added, control temperature of reaction 50 DEG C reaction 1 hour, add DMF50g and poly-hexanodioic acid-BDO esterdiol (molecular weight is 200) 126g, be heated to still temperature 75 DEG C and continue reaction, detect and reach 1.0 × 10 to reacting viscosity 5mPas/25 DEG C.
(8) add chainextender 1,6-hexylene glycol 9g, after DMF50g stirs 30min, add MDI19.07g and continue reaction, temperature controls at 75 DEG C, reacts 1 hour; Drop into catalyzer (bismuth catalyst 0.1g) reaction, add DMF75g and continue reaction, then detect viscosity, until viscosity reaches 1.0 × 10 5mPas/25 DEG C; Add methyl alcohol 0.14g and react 40min, discharging, obtains the urethane resin 650g that solid content is 50%.
The performance test results of urethane synthesized by each embodiment and corresponding contrast sample is as following table (only lacking POSS dibasic alcohol in the formula of contrast sample)
Illustrate:
1. the preparation method of test glued membrane: the first deaeration of obtained urethane resin, then coat on mirror surface release paper with 25 μm of gap rods, put into Electric heat oven drying, 80 DEG C are dried 20 minutes, and 120 DEG C are dried 30 minutes, totally 50 minutes.
2. glued membrane physical and mechanical properties testing method (100% answers stretch, tensile strength, elongation at break): according to GB/T528-2009 standard, adopts universal testing machine to carry out measuring (probe temperature is 25 DEG C, and rate of extension is 200mm/min).
3. softening temperature: the temperature that material is softening.Mainly refer to temperature when amorphous polymer starts deliquescing.The softening temperature of resin is measured by DSC.
4. contact angle: contact angle is used to exosyndrome material surface parent/hydrophobic one method simply and efficiently.The hydrophobicity of material surface is better, and its contact angle is larger.The test of contact angle adopts sessile drop method (Sessile drop method).At room temperature, by 10 μ l deionized water drop in mould material surface, by matching and calculating, obtain the static contact angle of sample, each sample parallel measures 6 times, obtains mean value, to reduce error.

Claims (9)

1. a preparation method for POSS modified polyurethane resin, is characterized in that comprising the following steps
(1) under nitrogen protection, add trihydroxy-seven successively and gather cage type siloxanes R 7si 8o 9(OH) 3, triethylamine and tetrahydrofuran (THF), then slowly inject SiCl 4after stirring is spent the night, cross and filter precipitation, filtrate rotary evaporation, obtain chlorination POSS:R 7si 8o 12cl, wherein R is i-C 4h 9, CH 3, C 6h 5in one;
(2) by chlorination POSS R 7si 8o 12cl refluxes 72-90h in the mixing solutions of tetrahydrofuran (THF) and water, after rotary evaporation desolventizes, obtains hydroxylation POSS R 7si 8o 12(OH);
(3) under nitrogen protection, hydroxylation POSS R is added successively 7si 8o 12(OH), tetrahydrofuran (THF), triethylamine, then slowly chlorodimethyl silane is added, 50-80 DEG C of reaction 15-20h, reaction product is transferred in separating funnel, use deionized water successively, after 5% hydrochloric acid soln and saturated NaCl solution are washed, filtrate is revolved and is steamed final vacuum drying, obtains alkylation POSS R 7si 8o 12si (CH 3) 2h;
(4) under nitrogen protection, Pt catalyzer is joined alkylation POSS R 7si 8o 12si (CH 3) 2in the toluene solution of H and Tetra Hydro Phthalic Anhydride THPA, 50-80 DEG C of reaction 40-70h, revolves the solid obtained after steaming desolventizes and adds in normal hexane, backflow 30min, cooling, filters, remove excessive Tetra Hydro Phthalic Anhydride, filtrate is revolved the solid after steaming and add activated carbon backflow 3h in acetone, the remaining Pt catalyzer of absorption removing, centrifugal, supernatant layer is collected, and revolves steaming, obtain white solid, reflux 2h in diacetyl oxide, revolves and steam final vacuum drying, obtain acid anhydrides POSSR 7si 8o 12si (CH 3) 2tHPA;
(5) by LiAlH 4tetrahydrofuran solution be slowly added drop-wise to acid anhydrides POSS R 7si 8o 12si (CH 3) 2in the tetrahydrofuran solution of THPA, reflux stir 1-3h at-10-10 DEG C after 10-20h; In reaction system, add soluble tartrate saturated aqueous solution of sodium until bubble-free effusion, continue backflow 10-20h, filter, by washed with diethylether precipitation, merge tetrahydrofuran (THF) and diethyl ether solution, anhydrous sodium sulfate drying, boils off solvent, obtains POSS dibasic alcohol;
(6) polyether Glycols, polyester diol and appropriate isocyanic ester are heated in a solvent carry out prepolymerization reaction;
(7) in the performed polymer that (6) step is obtained, add the obtained POSS dibasic alcohol of solvent, (5) step and chainextender, continue heating and make it react;
(8) in upper step reactant, add poly-dihydric alcohol continue reaction, and add solvent in reaction process, detecting the viscosity of resin, as reached default viscosity number, then adding solvent, terminator, terminate reaction; If do not reach default viscosity number, then add chainextender continue reaction, until add solvent when reaching default viscosity number, terminator terminate reaction.
2. the preparation method of POSS modified polyurethane resin as claimed in claim 1, the described trihydroxy-seven that it is characterized in that in (1) step gathers that cage type siloxanes is that trihydroxy-seven isobutyl-seven gathers cage type siloxanes, trihydroxy-seven methyl seven gathers cage type siloxanes, trihydroxy-seven phenyl seven gathers one in cage type siloxanes; R 7si 8o 9(OH) 3with SiCl 4mol ratio be 1: (1 ~ 1.5).
3. the preparation method of POSS modified polyurethane resin as claimed in claim 1 or 2, is characterized in that the described R in (3) step 7si 8o 12(OH) be 1 with the mol ratio of chlorodimethyl silane: (1 ~ 1.3).
4. the preparation method of POSS modified polyurethane resin as claimed in claim 3, is characterized in that the described R in (4) step 7si 8o 12si (CH 3) 2the mol ratio of H and Tetra Hydro Phthalic Anhydride is 1: (1 ~ 1.1).
5. the preparation method of POSS modified polyurethane resin as claimed in claim 4, is characterized in that the described R in (5) step 7si 8o 12si (CH 3) 2tHPA and LiAlH 4mol ratio be 1: (2 ~ 4).
6. the preparation method of POSS modified polyurethane resin as claimed in claim 5, it is characterized in that the described isocyanic ester in (6) step is 4, one or more in 4 '-diphenylmethanediisocyanate, tolylene diisocyanate, isophorone diisocyanate, hydrogenated diphenyl methane diisocyanate or 1,6-hexamethylene diisocyanate; Described polyether Glycols is one or more in polyoxyethylene glycol, polyoxypropyleneglycol or PTMG, and molecular weight is 1000 ~ 4000; Described polyester polyol is one or more in polyethylene glycol adipate glycol, poly-hexanodioic acid-BDO esterdiol, polyhexamethylene adipate glycol or polycarbonate diol, and molecular weight is 1000 ~ 4000; Described isocyanic ester and the mol ratio of poly-dihydric alcohol are (1.2 ~ 2): 1, and temperature of reaction is 60 ~ 100 DEG C.
7. the preparation method of POSS modified polyurethane resin as claimed in claim 6, the described solvent that it is characterized in that in (6) step is one or more in dimethyl formamide, butanone, toluene, ethyl acetate.
8. the preparation method of POSS modified polyurethane resin as claimed in claim 7, it is characterized in that the chainextender described in (7) step is ethylene glycol, 1,4-butyleneglycol, 1,6-hexylene glycol, glycol ether, neopentyl glycol or 2-methyl isophthalic acid, one or more in ammediol; Described POSS dibasic alcohol and the weight ratio of performed polymer are: (1 ~ 8): 100, and the weight ratio of chainextender and performed polymer is (3 ~ 20): 100, and temperature of reaction is 40 ~ 70 DEG C.
9. the preparation method of POSS modified polyurethane emulsion as claimed in claim 8, it is characterized in that the terminator described in (8) step be molecular weight be less than in the single methanol of 500g/mol, monoamine one or more.
CN201310529272.6A 2013-10-31 2013-10-31 Preparation method of POSS modified polyurethane resin Pending CN104592473A (en)

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CN108192073A (en) * 2017-12-23 2018-06-22 广东互典缓冲材料技术有限公司 Padded coaming that a kind of wide temperature range domain uses and its preparation method and application
CN109575221A (en) * 2018-12-04 2019-04-05 镇江利德尔复合材料有限公司 A kind of polyurethane shape memory material and preparation method thereof strengthened based on organosilicon polymer
CN110294832B (en) * 2019-07-16 2021-05-25 道勤材料技术(麻城)有限公司 Amino POSS modified polyurethane thermoplastic elastomer and preparation method thereof
CN110294832A (en) * 2019-07-16 2019-10-01 道勤材料技术(麻城)有限公司 A kind of polyurethane termoplastic elastomer and preparation method thereof of amino POSS modification
CN110669198A (en) * 2019-10-15 2020-01-10 浙江禾欣科技有限公司 Solvent-free polyurethane resin for POSS (polyhedral oligomeric silsesquioxane) -based automobile leather and preparation method thereof
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CN114085355A (en) * 2020-08-24 2022-02-25 万华化学集团股份有限公司 High-strength hydrolysis-resistant thermoplastic polyurethane elastomer material, preparation method and application
CN113509034A (en) * 2021-06-25 2021-10-19 华鸿画家居股份有限公司 Texture paper frame strip
CN113509034B (en) * 2021-06-25 2022-09-20 华鸿画家居股份有限公司 Texture paper frame strip
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Application publication date: 20150506