CN110790893A - Method for improving toughness and flame retardant property of polyisocyanurate - Google Patents
Method for improving toughness and flame retardant property of polyisocyanurate Download PDFInfo
- Publication number
- CN110790893A CN110790893A CN201911143809.9A CN201911143809A CN110790893A CN 110790893 A CN110790893 A CN 110790893A CN 201911143809 A CN201911143809 A CN 201911143809A CN 110790893 A CN110790893 A CN 110790893A
- Authority
- CN
- China
- Prior art keywords
- pdms
- triblock copolymer
- pvp
- pmma
- reaction
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
Images
Classifications
-
- 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
- C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
- C08G18/72—Polyisocyanates or polyisothiocyanates
- C08G18/74—Polyisocyanates or polyisothiocyanates cyclic
- C08G18/76—Polyisocyanates or polyisothiocyanates cyclic aromatic
- C08G18/7657—Polyisocyanates or polyisothiocyanates cyclic aromatic containing two or more aromatic rings
- C08G18/7664—Polyisocyanates or polyisothiocyanates cyclic aromatic containing two or more aromatic rings containing alkylene polyphenyl groups
- C08G18/7671—Polyisocyanates or polyisothiocyanates cyclic aromatic containing two or more aromatic rings containing alkylene polyphenyl groups containing only one alkylene bisphenyl group
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F293/00—Macromolecular compounds obtained by polymerisation on to a macromolecule having groups capable of inducing the formation of new polymer chains bound exclusively at one or both ends of the starting macromolecule
-
- 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
- C08G18/4072—Mixtures of compounds of group C08G18/63 with other macromolecular compounds
-
- 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
-
- 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
- C08G18/63—Block or graft polymers obtained by polymerising compounds having carbon-to-carbon double bonds on to polymers
Landscapes
- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Polyurethanes Or Polyureas (AREA)
Abstract
The invention belongs to the field of modification of high molecular resin, and particularly relates to application of polydimethylsiloxane in toughening polyisocyanurate and improving flame retardant property. The expressions for the three block copolymers are: PVP-b-PDMS-b-PVP, PS-b-PDMS-b-PS and PMMA-b-PDMS-b-PMMA, wherein PDMS is polydimethylsilane, PVP is polyvinylpyrrolidone, PS is polystyrene, and PMMA is polymethyl methacrylate. The molecular weight of the triblock copolymer is 8000-50000g/mol, wherein the molecular weight of PDMS is 1000-6000 g/mol. According to the invention, the three block copolymers are respectively mixed into the polyisocyanurate to respectively obtain uniformly dispersed PDMS nano microphase structures, so that the polyisocyanurate toughening effect is obvious and the flame retardant property of the polyisocyanurate is improved to a certain extent.
Description
Technical Field
The invention belongs to the field of modification of high molecular resin, and particularly relates to application of polydimethylsiloxane in toughening polyisocyanurate and improving flame retardant property.
Background
The polyisocyanurate is an engineering high polymer material with excellent performance, has the widely known advantages of excellent chemical stability, dimensional stability, high specific strength and the like, particularly has ultralow heat conductivity coefficient, and is widely applied to heat insulation in the fields of daily life, cold chain transportation, LNG pipelines, aerospace and the like. The ultra-low heat-conducting property of the polyisocyanurate is derived from a special ring structure in a molecular chain of the polyisocyanurate, the structure enables the molecular chain to have rigidity, and the heat-conducting property of the material is reduced, but the toughness of the polyisocyanurate is reduced due to the rigid molecular structure. Meanwhile, polyisocyanurate foam is easy to burn, a large amount of toxic gas can be generated after the polyisocyanurate foam burns, and due to the low thermal conductivity and the large porosity of the polyisocyanurate foam, the polyisocyanurate foam is difficult to self-extinguish after the polyisocyanurate foam burns.
The polydimethylsiloxane is a high-molecular chain which is very flexible, the viscosity is less changed along with the temperature, the polydimethylsiloxane can be stably used at the temperature of minus 50-200 ℃ for a long time, and meanwhile, as the main chain contains a large amount of silicon elements, the polydimethylsiloxane has excellent flame retardant property, and the polydimethylsiloxane can simultaneously play the effects of toughening and improving the flame retardant property by uniformly dispersing the polydimethylsiloxane in polyisocyanurate. But because polydimethylsiloxane and polyisocyanurate are thermodynamically incompatible, the polydimethylsiloxane and polyisocyanurate can not be directly and uniformly dispersed in polyisocyanurate, in order to solve the problem, the invention prepares the polydimethylsiloxane, polyvinylpyrrolidone, polystyrene, polymethyl methacrylate and other polymers with better compatibility with polyisocyanurate into ABA type triblock copolymer, and obtains the polyisocyanurate composite material containing the polydimethylsiloxane nano structure for the first time by utilizing the compatibility of the segmented copolymer and the polyisocyanurate.
Disclosure of Invention
The invention aims to solve the problems that the polyisocyanurate is low in toughness and easy to crack under the action of external force at low temperature, and simultaneously improve the thermal stability of the polyisocyanurate. The invention provides a preparation method of polyisocyanurate modified by triblock copolymer of polydimethylsiloxane, which is characterized in that polyvinylpyrrolidone (PVP), Polystyrene (PS) or polymethyl methacrylate (PMMA) and Polydimethylsiloxane (PDMS) are respectively prepared into ABA type triblock copolymer by different polymerization methods. The polydimethylsiloxane chain segment has the effects of toughening and improving the thermal stability of Polyisocyanurate (PIR), and the polyvinylpyrrolidone, polystyrene or polymethyl methacrylate chain segment has good compatibility with the PIR, so that the dispersion effect of Polydimethylsiloxane (PDMS) in the PIR can be improved, and meanwhile, the Polydimethylsiloxane (PDMS) nano microphase can be stabilized, the microphase aggregation is prevented, the stability of the microstructure of the material is improved, and the service life of the polyisocyanurate composite material is prolonged. The PVP-b-PDMS-b-PVP triblock copolymer is mixed into the polyisocyanurate, so that the toughness of the polyisocyanurate is improved by more than 4 times, and the thermal decomposition temperature is improved by more than 5 ℃; after the PS-b-PDMS-b-PS triblock copolymer is mixed into the polyisocyanurate, the toughness of the polyisocyanurate is improved by more than 2 times, and the thermal decomposition temperature is improved by more than 8 ℃; after the PMMA-b-PDMS-b-PMMA triblock copolymer is mixed into the polyisocyanurate, the toughness of the polyisocyanurate is improved by more than 3 times, and the thermal decomposition temperature is improved by more than 11 ℃.
According to a first aspect of the present invention, there is provided a polydimethylsiloxane-containing triblock copolymer modified polyisocyanurate, the polydimethylsiloxane-containing triblock copolymer having polydimethylsiloxane as block B of an ABA type triblock copolymer and polyvinylpyrrolidone as block a to form a PVP-B-PDMS-B-PVP triblock copolymer, or polystyrene as block a to form a PS-B-PDMS-B-PS triblock copolymer, or polymethylmethacrylate as block a to form a PMMA-B-PDMS-B-PMMA triblock copolymer;
the structural formula of the PVP-b-PDMS-b-PVP triblock copolymer is shown as the formula (1):
the structural formula of the PS-b-PDMS-b-PS triblock copolymer is shown as the formula (2):
the structural formula of the PMMA-b-PDMS-b-PMMA triblock copolymer is shown as the formula (3):
the ratio of m to n in the structural formulas (1) to (3) is 1:0.25 to 1: 3.
Preferably, the molecular weight of the corresponding structures of the structural formulas (1) to (3) is 8000-50000 g/mol; the molecular weight of the polydimethylsilane is 1000-6000 g/mol.
According to a second aspect of the present invention, there is provided a process for the preparation of a polydimethylsiloxane containing tri-block copolymer modified polyisocyanurate comprising:
mixing polyether polyol mixture, isocyanate and any block copolymer of PVP-b-PDMS-b-PVP block copolymer, PS-b-PDMS-b-PS block copolymer or PMMA-b-PDMS-b-PMMA block copolymer according to a certain mass ratio, stirring uniformly, pouring into a mold for curing, demolding and curing at high temperature to obtain the polyisocyanurate modified by the triblock copolymer containing polydimethylsiloxane;
the PVP-b-PDMS-b-PVP triblock copolymer is prepared by the following method: mixing PDMS (PDMS-OH) with hydroxyl end capping at two ends, ethylxanthic acid (XA), Dicyclohexylcarbodiimide (DCC), 4-Dimethylaminopyridine (DMAP) and dichloromethane according to a certain molar ratio, adding the mixture into a reaction kettle, stirring and reacting at room temperature, washing a product for three times after the reaction is finished, and separating and concentrating the liquid to obtain PDMS (PDMS-X) with ethylxanthic end capping; mixing PDMS (PDMS-X) with an ethyl xanthate end cap, vinyl pyrrolidone, Azobisisobutyronitrile (AIBN) and 1, 4-dioxane according to a certain molar ratio, adding the mixture into a reaction kettle, introducing nitrogen into a reaction system, heating, stirring, reacting, concentrating a product after the reaction is finished, dropping the product into petroleum ether, precipitating and purifying to obtain a PVP-b-PDMS-b-PVP triblock copolymer;
the PS-b-PDMS-b-PS triblock copolymer is prepared by the following method: mixing PDMS (PDMS-OH) with two end hydroxyl end caps, 2-bromopropionyl bromide, triethylamine and dichloromethane according to a certain molar ratio, reacting under an ice bath condition, removing precipitates after the reaction is finished, and purifying to obtain 2- (2-bromoacrylate) methyl end cap PDMS (PDMS-Br); mixing 2- (2-bromoacrylate) methyl-terminated PDMS (PDMS-Br), styrene, cuprous bromide, N, N, N ', N ', N ' -pentamethyldiethylenetriamine and toluene according to a certain molar ratio, adding the mixture into a reaction kettle, introducing nitrogen into a reaction system, heating for reaction, concentrating a product after the reaction is finished, and precipitating and purifying in methanol to obtain a PS-b-PDMS-b-PS triblock copolymer;
the PMMA-b-PDMS-b-PMMA triblock copolymer is prepared by the following method: mixing PDMS (PDMS-OH) with hydroxyl end caps at two ends, 2- (dodecyl trithiocarbonate) -2-methylpropanoic acid (CTA), 1- (3-dimethylaminopropyl) -3-ethylcarbodiimide hydrochloride (EDC), 4-Dimethylaminopyridine (DMAP) and dichloromethane according to a certain molar ratio, adding the mixture into a reaction kettle to react at room temperature, and separating and purifying the liquid after the reaction is finished to obtain the PDMS (PDMS-CTA) with the end caps of the 2- (dodecyl trithiocarbonate) -2-methylpropanoic acid; mixing 2- (dodecyl trithiocarbonate) -2-methylpropanoic acid-terminated PDMS (PDMS-CTA), methyl methacrylate, Azobisisobutyronitrile (AIBN) and 1, 4-dioxane according to a certain molar ratio, adding the mixture into a reaction kettle, introducing nitrogen into a reaction system, heating for reaction, and precipitating and purifying a product in methanol after the reaction is finished to obtain the PMMA-b-PDMS-b-PMMA triblock copolymer.
Preferably, the polyether polyol mixture has a viscosity of 3000-4000mPa.s, a hydroxyl value of 350-450mgKOH/gOil and a moisture content of less than 1.0%.
Preferably, the polyether polyol mixture is prepared by stirring the following materials in parts by weight at room temperature: 2 parts of polypropylene glycol with the hydroxyl value of 320-380mgKOH/gOil and the average molecular weight of 580g/mol, 6 parts of polypropylene glycol with the hydroxyl value of 430-460mgKOH/gOil and the average molecular weight of 220g/mol, 8 parts of phthalic anhydride polyester polyol with the hydroxyl value of 100-220mgKOH/gOil and the viscosity of 4000-8000mPa.s, and 0.3 part of catalyst; the catalyst is a mixture of 2 parts triethylenediamine and 1 part potassium acetate.
Preferably, the molar ratio of PDMS with two hydroxyl end caps, ethylxanthic acid, dicyclohexylcarbodiimide, 4-dimethylaminopyridine and dichloromethane in the preparation method of the PVP-b-PDMS-b-PVP triblock copolymer is 1:10-20:10-20:1-2: 10000-30000; the molar ratio of the ethyl xanthyl terminated PDMS, the vinyl pyrrolidone, the azodiisobutyronitrile and the 1, 4-dioxane is 1:45-225:0.4-0.7: 1100-;
preferably, the molar ratio of PDMS with two end hydroxyl groups blocked, 2-bromopropionyl bromide, triethylamine and dichloromethane in the preparation method of the PS-b-PDMS-b-PS triblock copolymer is 1:5-10:2-5: 10000-30000; the molar ratio of 2- (2-bromoacrylate) methyl-terminated PDMS, styrene, cuprous bromide, N, N, N ', N ', N ' -pentamethyldiethylenetriamine and toluene is 1:45-225:1-2:1-2: 1100-;
preferably, in the preparation method of the PMMA-b-PDMS-b-PMMA triblock copolymer, the molar ratio of PDMS with two hydroxyl groups blocked at two ends, 2- (dodecyl trithiocarbonate) -2-methylpropanoic acid, 1- (3-dimethylaminopropyl) -3-ethylcarbodiimide hydrochloride, 4-dimethylaminopyridine and dichloromethane is 1:10-20:10-20:1-2: 10000-30000; the molar ratio of the 2- (dodecyl trithiocarbonate) -2-methylpropanoic acid terminated PDMS to the methyl methacrylate to the azodiisobutyronitrile to the 1, 4-dioxane is 1:45-225:0.4-0.7: 1100-.
Preferably, the mass ratio of the polyether polyol mixture, the isocyanate and the block copolymer is 100:150-200:15-25: 12.5-105.
Preferably, the isocyanate is 4,4' -methylenebis (phenyl isocyanate) and has an NCO value of 31%.
The ABA type triblock copolymer is prepared by polyvinylpyrrolidone (PVP), Polystyrene (PS) or polymethyl methacrylate (PMMA) and Polydimethylsiloxane (PDMS) for the first time, is used for modifying polyisocyanurate, and has the following advantages compared with the conventional polyisocyanurate:
(1) the modified polyisocyanurate composite material prepared by the invention has a PDMS nano microphase structure with uniformly dispersed ABA type triblock copolymer;
(2) the modified polyisocyanurate composite material prepared by the invention has a remarkable toughening effect and improves the flame retardant property of polyisocyanurate to a certain extent;
(3) the modified polyisocyanurate composite material prepared by the invention not only solves the problems of low toughness of polyisocyanurate and easy fragmentation under the action of external force at low temperature, but also improves the thermal stability of polyisocyanurate.
Drawings
FIG. 1 is a transmission electron micrograph of PVP-b-PDMS-b-PVP modified polyisocyanurate composite prepared in example 1 of this invention.
FIG. 2 is a transmission electron microscope image of the PS-b-PDMS-b-PS modified polyisocyanurate composite prepared in example 2 of the present invention.
FIG. 3 is a transmission electron microscope image of PMMA-b-PDMS-b-PMMA modified polyisocyanurate composite prepared in example 3 of the present invention.
FIG. 4 shows PVP-b-PDMS-b-PVP and intermediate products prepared in example 1 of the present invention1H nuclear magnetic spectrum.
FIG. 5 shows the preparation of PS-b-PDMS-b-PS and intermediates of example 2 of the present invention1H nuclear magnetic spectrum.
FIG. 6 shows PMMA-b-PDMS-b-PMMA and intermediate products prepared by example 3 of the present invention1H nuclear magnetic spectrum.
The black spherical phase in fig. 1-3 is a nano structure formed by polydimethylsiloxane, and the nano structure plays a role in toughening and improving the flame retardant property.
Detailed Description
PDMS-OH: molecular weight of 5000g/mol, as supplied by Degussa China company; polypropylene glycol: provided by Nantong Hancheng chemical Co., Ltd., hydroxyl value is 320mgKOH/gOil, molecular weight is 400g/mol, hydroxyl value is 460mgKOH/gOil, molecular weight is 180 g/mol; phthalic anhydride polyester polyol: supplied by Qingdao Renol chemical Co., Ltd., a hydroxyl value of 175mgKOH/gOil and a viscosity of 5000 mPa.s.
The self-made polyether polyol mixture is prepared by stirring the following materials in parts by weight at room temperature: 2 parts of polypropylene glycol with the hydroxyl value of 320-380mgKOH/gOil and the average molecular weight of 580g/mol, 6 parts of polypropylene glycol with the hydroxyl value of 430-460mgKOH/gOil and the average molecular weight of 220g/mol, 8 parts of phthalic anhydride polyester polyol with the hydroxyl value of 100-220mgKOH/gOil and the viscosity of 4000-8000mPa.s, and 0.3 part of catalyst; the catalyst is a mixture of 2 parts triethylenediamine and 1 part potassium acetate. The viscosity of the prepared polyether polyol mixture is 3000-4000mPa.s, the hydroxyl value is 350-450mgKOH/gOil, and the water content is less than 1.0 percent.
Example 1
Preparing a PVP-b-PDMS-b-PVP modified polyisocyanurate composite material:
(1) preparation of PVP-b-PDMS-b-PVP
5.2g of PDMS-OH (Mn is 5000g/mol), 3.1g of potassium ethyl xanthate, 2.8g of dicyclohexylcarbodiimide, 0.21g of 4-dimethylaminopyridine and 100g of dichloromethane are weighed and added into a reaction kettle, the mixture is stirred at room temperature for 24 hours to react, impurities generated in the reaction are filtered, the solution is washed for three times, and the solvent is removed by rotary evaporation and dried to obtain PDMS-X. Weighing 3.2g of PDMS-X, 7.8g of vinyl pyrrolidone, 0.052g of azobisisobutyronitrile, 20g of 1, 4-dioxane, adding into a reaction kettle, introducing nitrogen into the reaction kettle for 30 minutes, sealing, stirring at the reaction temperature of 60 ℃ for 12 hours to obtain a product, concentrating the product, dropwise adding into petroleum ether for washing for three times, collecting the precipitate, and drying to obtain the PVP-b-PDMS-b-PVP triblock copolymer with the molecular weight of 14200 g/mol. The nuclear magnetic spectrum of PDMS-OH, PDMS-X and its PVP-b-PDMS-b-PVP triblock copolymer is shown in FIG. 4.
(2) Preparation of polyisocyanurate blends containing PVP-b-PDMS-b-PVP
Weighing 50.2g of polyether polyol mixture, 75.4g of 4,4' -methylenebis (phenyl isocyanate) and 12.9g of PVP-b-PDMS-b-PVP triblock copolymer, mechanically stirring for 2 minutes, pouring into a mold, curing at 90 ℃ for 15 minutes, demolding, and curing at 150 ℃ for 2 hours to obtain a polyisocyanurate blend (as shown in a transmission electron microscope picture in figure 1), wherein the mass content of the block copolymer PVP-b-PDMS-b-PVP is 10.3%.
Example 2
Preparing a PVP-b-PDMS-b-PVP modified polyisocyanurate composite material:
(1) preparation of PS-b-PDMS-b-PS
5.5g of PDMS-OH (Mn is 5000g/mol), 6.2g of 2-bromopropionyl bromide, 2.1g of triethylamine and 100g of dichloromethane are weighed and added into a reaction kettle, the mixture is stirred and reacted for 24 hours under the ice bath condition, impurities generated in the reaction are filtered, dichloromethane solution is washed for three times, and the solvent is dried by rotary evaporation to obtain PDMS-Br. Adding 3.1g of PDMS-Br, 8.1g of styrene, 0.035g of cuprous bromide, 0.021g N, N, N ', N ', N ' -pentamethyldiethylenetriamine and 20g of toluene into a reaction kettle, introducing nitrogen into the reaction kettle for thirty minutes, sealing, stirring at the reaction temperature of 85 ℃ for 12 hours to obtain a product, concentrating the product, dropwise adding the product into methanol for washing for three times, collecting the precipitate, and drying to obtain the PS-b-PDMS-b-PS triblock copolymer with the molecular weight of 15400 g/mol. The nuclear magnetic spectrum of the PDMS-OH, PDMS-Br and PS-b-PDMS-b-PS triblock copolymer is shown in FIG. 5
(2) Preparation of polyisocyanurate blends containing PS-b-PDMS-b-PS
Weighing 50.5g of polyether polyol mixture, 75.2g of 4,4' -methylenebis (phenyl isocyanate) and 13.3g of PS-b-PDMS-b-PS triblock copolymer, mechanically stirring for 2 minutes, pouring into a mold, curing at 90 ℃ for 15 minutes, demolding, and curing at 150 ℃ for 2 hours to obtain a final product (shown in a transmission electron microscope picture as figure 2), wherein the mass content of the block copolymer PS-b-PDMS-b-PS is 10.6%.
Example 3
Preparing a PMMA-b-PDMS-b-PMMA modified polyisocyanurate composite material:
(1) preparation of PMMA-b-PDMS-b-PMMA
5.1g of PDMS-OH (Mn ═ 5000g/mol), 3.2g of 2- (dodecyl trithiocarbonate) -2-methylpropanoic acid, 2.4g of 1- (3-dimethylaminopropyl) -3-ethylcarbodiimide hydrochloride, 0.18g of 4-dimethylaminopyridine and 100g of dichloromethane are weighed, added into a reaction kettle, stirred at room temperature for reaction for 24 hours, impurities generated in the reaction are filtered, a dichloromethane solution is washed with water for three times, and the solvent is dried by rotary evaporation to obtain PDMS-CTA. Adding 3.0g of PDMS-CTA, 7.6g of methyl methacrylate, 0.048g of azobisisobutyronitrile, 20g of 1, 4-dioxane into a reaction kettle, introducing nitrogen into the reaction kettle for thirty minutes, sealing, stirring at the reaction temperature of 80 ℃ for 12 hours to obtain a product, concentrating the product, dropwise adding the product into methanol for washing three times, collecting the precipitate, and drying to obtain the PMMA-b-PDMS-b-PMMA triblock copolymer with the molecular weight of 16100 g/mol. The nuclear magnetic hydrogen spectrum of PDMS-OH, PDMS-CTA and PMMA-b-PDMS-b-PMMA triblock copolymer is shown in FIG. 6.
(2) Preparation of polyisocyanurate blends containing PMMA-b-PDMS-b-PMMA
Weighing 50.1g of polyether polyol mixture, 75.3g of 4,4' -methylenebis (phenyl isocyanate) and 12.8g of PMMA-b-PDMS-b-PMMA triblock copolymer, mechanically stirring for 2 minutes, pouring into a mold, curing for 15 minutes at 90 ℃, demolding, and curing for 2 hours at 150 ℃ to obtain a final product (shown in a transmission electron microscope picture as figure 3), wherein the mass content of the block copolymer PMMA-b-PDMS-b-PMMA is 10.2%.
Comparative example
Compared with the polyisocyanurate without the PDMS triblock copolymer, the polyisocyanurate prepared by the invention has the same raw materials, proportion and process as those of the polyisocyanurate prepared by the embodiment.
The break toughness of the polyisocyanurate was tested according to ISO 13586, the water contact angle of the polyisocyanurate according to GB/T30639, the thermal conductivity of the polyisocyanurate according to GB10294, the thermal stability of the polyisocyanurate according to its initial thermal decomposition temperature in an air atmosphere was quantitatively characterized and the results are reported in table 1:
TABLE 1 Properties of the products prepared in the different examples
The above embodiments are preferred embodiments of the present invention, but the present invention is not limited to the above embodiments, and any other changes, modifications, substitutions, combinations, and simplifications which do not depart from the spirit and principle of the present invention should be construed as equivalents thereof, and all such changes, modifications, substitutions, combinations, and simplifications are intended to be included in the scope of the present invention.
Claims (8)
1. A polydimethylsiloxane-containing tri-block copolymer modified polyisocyanurate comprising: the triblock copolymer containing the polydimethylsiloxane takes the polydimethylsiloxane as a block B of an ABA type triblock copolymer, takes polyvinylpyrrolidone as a block A to form a PVP-B-PDMS-B-PVP triblock copolymer, or takes polystyrene as the block A to form a PS-B-PDMS-B-PS triblock copolymer, or takes polymethyl methacrylate as the block A to form a PMMA-B-PDMS-B-PMMA triblock copolymer;
the structural formula of the PVP-b-PDMS-b-PVP triblock copolymer is shown as the formula (1):
the structural formula of the PS-b-PDMS-b-PS triblock copolymer is shown as the formula (2):
the structural formula of the PMMA-b-PDMS-b-PMMA triblock copolymer is shown as the formula (3):
the ratio of m to n in the structural formulas (1) to (3) is 1:0.25 to 1: 3.
2. The polydimethylsiloxane-containing triblock copolymer-modified polyisocyanurate according to claim 1, wherein: the molecular weight of the corresponding structures of the structural formulas (1) - (3) is 8000-50000 g/mol; the molecular weight of the polydimethylsilane is 1000-6000 g/mol.
3. A process for preparing a polydimethylsiloxane-containing triblock copolymer-modified polyisocyanurate as described in claim 1, wherein said process comprises:
mixing polyether polyol mixture, isocyanate and any block copolymer of PVP-b-PDMS-b-PVP block copolymer, PS-b-PDMS-b-PS block copolymer or PMMA-b-PDMS-b-PMMA block copolymer according to a certain mass ratio, stirring uniformly, pouring into a mold for curing, demolding and curing at high temperature to obtain the polyisocyanurate modified by the triblock copolymer containing polydimethylsiloxane;
the PVP-b-PDMS-b-PVP triblock copolymer is prepared by the following method: mixing PDMS with two end hydroxyl groups blocked, ethyl xanthic acid, dicyclohexylcarbodiimide, 4-dimethylaminopyridine and dichloromethane according to a certain molar ratio, adding the mixture into a reaction kettle, stirring at room temperature for reaction, washing a product for three times after the reaction is finished, and separating and concentrating the liquid to obtain PDMS with an ethyl xanthic group blocked; mixing PDMS (polydimethylsiloxane), vinyl pyrrolidone, azodiisobutyronitrile and 1, 4-dioxane which are blocked by ethyl xanthyl according to a certain molar ratio, adding the mixture into a reaction kettle, introducing nitrogen into a reaction system, heating and stirring for reaction, concentrating a product after the reaction is finished, and then dripping the product into petroleum ether for precipitation and purification to obtain a PVP-b-PDMS-b-PVP triblock copolymer;
the PS-b-PDMS-b-PS triblock copolymer is prepared by the following method: mixing PDMS with two end hydroxyl end caps, 2-bromopropionyl bromide, triethylamine and dichloromethane according to a certain molar ratio, reacting under an ice bath condition, removing precipitates after the reaction is finished, and purifying to obtain 2- (2-bromoacrylate) methyl end cap PDMS; mixing 2- (2-bromoacrylate) methyl-terminated PDMS, styrene, cuprous bromide, N, N, N ', N ', N ' -pentamethyldiethylenetriamine and toluene according to a certain molar ratio, adding the mixture into a reaction kettle, introducing nitrogen into a reaction system, heating for reaction, concentrating a product after the reaction is finished, and precipitating and purifying in methanol to obtain a PS-b-PDMS-b-PS triblock copolymer;
the PMMA-b-PDMS-b-PMMA triblock copolymer is prepared by the following method: mixing PDMS with two hydroxyl end caps, 2- (dodecyl trithiocarbonate) -2-methylpropanoic acid, 1- (3-dimethylaminopropyl) -3-ethylcarbodiimide hydrochloride, 4-dimethylaminopyridine and dichloromethane according to a certain molar ratio, adding the mixture into a reaction kettle to react at room temperature, and separating and purifying after the reaction is finished to obtain the PDMS with the 2- (dodecyl trithiocarbonate) -2-methylpropanoic acid end caps; mixing 2- (dodecyl trithiocarbonate) -2-methylpropanoic acid-terminated PDMS, methyl methacrylate, azodiisobutyronitrile and 1, 4-dioxane according to a certain molar ratio, adding the mixture into a reaction kettle, introducing nitrogen into a reaction system, heating for reaction, and precipitating and purifying a product in methanol after the reaction is finished to obtain the PMMA-b-PDMS-b-PMMA triblock copolymer.
4. The method of claim 3, wherein: the polyether polyol mixture has a viscosity of 3000-4000mPa.s, a hydroxyl value of 350-450mgKOH/gOil and a water content of less than 1.0%.
5. The method of claim 3, wherein: the polyether polyol mixture is prepared by stirring the following materials in parts by weight at room temperature: 2 parts of polypropylene glycol with the hydroxyl value of 320-380mgKOH/gOil and the average molecular weight of 580g/mol, 6 parts of polypropylene glycol with the hydroxyl value of 430-460mgKOH/gOil and the average molecular weight of 220g/mol, 8 parts of phthalic anhydride polyester polyol with the hydroxyl value of 100-220mgKOH/gOil and the viscosity of 4000-8000mPa.s, and 0.3 part of catalyst; the catalyst is a mixture of 2 parts triethylenediamine and 1 part potassium acetate.
6. The method of claim 3, wherein:
the preparation method of the PVP-b-PDMS-b-PVP triblock copolymer comprises the following steps that the molar ratio of PDMS with two end hydroxyl groups blocked, ethyl xanthic acid, dicyclohexyl carbodiimide, 4-dimethylamino pyridine and dichloromethane is 1:10-20:10-20:1-2: 10000-30000; the molar ratio of the ethyl xanthyl terminated PDMS, the vinyl pyrrolidone, the azodiisobutyronitrile and the 1, 4-dioxane is 1:45-225:0.4-0.7: 1100-;
the molar ratio of PDMS with two end hydroxyl end-capped ends, 2-bromopropionyl bromide, triethylamine and dichloromethane in the preparation method of the PS-b-PDMS-b-PS triblock copolymer is 1:5-10:2-5: 10000-30000; the molar ratio of 2- (2-bromoacrylate) methyl-terminated PDMS, styrene, cuprous bromide, N, N, N ', N ', N ' -pentamethyldiethylenetriamine and toluene is 1:45-225:1-2:1-2: 1100-;
in the preparation method of the PMMA-b-PDMS-b-PMMA triblock copolymer, the molar ratio of PDMS with two end hydroxyl groups blocked, 2- (dodecyl trithiocarbonate) -2-methylpropionic acid, 1- (3-dimethylaminopropyl) -3-ethylcarbodiimide hydrochloride, 4-dimethylaminopyridine and dichloromethane is 1:10-20:10-20:1-2: 10000-30000; the molar ratio of the 2- (dodecyl trithiocarbonate) -2-methylpropanoic acid terminated PDMS to the methyl methacrylate to the azodiisobutyronitrile to the 1, 4-dioxane is 1:45-225:0.4-0.7: 1100-.
7. The method of claim 3, wherein: the mass ratio of the polyether polyol mixture, the isocyanate and the block copolymer is 100:150-200:15-25: 12.5-105.
8. The method of claim 3, wherein: the isocyanate was 4,4' -methylenebis (phenyl isocyanate) and had an NCO value of 31%.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201911143809.9A CN110790893B (en) | 2019-11-20 | 2019-11-20 | Method for improving toughness and flame retardant property of polyisocyanurate |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201911143809.9A CN110790893B (en) | 2019-11-20 | 2019-11-20 | Method for improving toughness and flame retardant property of polyisocyanurate |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN110790893A true CN110790893A (en) | 2020-02-14 |
| CN110790893B CN110790893B (en) | 2021-12-28 |
Family
ID=69445585
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201911143809.9A Active CN110790893B (en) | 2019-11-20 | 2019-11-20 | Method for improving toughness and flame retardant property of polyisocyanurate |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN110790893B (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113943054A (en) * | 2021-10-25 | 2022-01-18 | 常熟理工学院 | Method for efficiently cleaning fluorine-containing micro-plastic in water body by using spirulina |
| CN115466585A (en) * | 2021-12-25 | 2022-12-13 | 闽南师范大学 | Lignin-based waterborne polyurethane-acrylate wood adhesive and preparation method thereof |
Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20020037965A1 (en) * | 1999-09-09 | 2002-03-28 | Hideo Kinoshita | High impact thermoplastic resin composition |
| CN103665316A (en) * | 2013-12-09 | 2014-03-26 | 山东一诺威聚氨酯股份有限公司 | Preparation method of organic silicon modified MDI |
| CN104403301A (en) * | 2014-09-05 | 2015-03-11 | 东莞市瀛通电线有限公司 | Self-cleaning material for signal lines and preparation method thereof |
| CN105377930A (en) * | 2013-05-31 | 2016-03-02 | 亨茨曼国际有限公司 | A method for improving toughness of polyisocyanate polyaddition reaction products |
| CN106795270A (en) * | 2014-09-05 | 2017-05-31 | 亨茨曼国际有限公司 | The method for improving the fracture toughness of the product comprising poly-isocyanurate |
| CN108137774A (en) * | 2015-08-07 | 2018-06-08 | 亨茨曼国际有限公司 | The method for improving the fracture toughness of the reaction product comprising poly-isocyanurate |
-
2019
- 2019-11-20 CN CN201911143809.9A patent/CN110790893B/en active Active
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20020037965A1 (en) * | 1999-09-09 | 2002-03-28 | Hideo Kinoshita | High impact thermoplastic resin composition |
| CN105377930A (en) * | 2013-05-31 | 2016-03-02 | 亨茨曼国际有限公司 | A method for improving toughness of polyisocyanate polyaddition reaction products |
| CN103665316A (en) * | 2013-12-09 | 2014-03-26 | 山东一诺威聚氨酯股份有限公司 | Preparation method of organic silicon modified MDI |
| CN104403301A (en) * | 2014-09-05 | 2015-03-11 | 东莞市瀛通电线有限公司 | Self-cleaning material for signal lines and preparation method thereof |
| CN106795270A (en) * | 2014-09-05 | 2017-05-31 | 亨茨曼国际有限公司 | The method for improving the fracture toughness of the product comprising poly-isocyanurate |
| CN108137774A (en) * | 2015-08-07 | 2018-06-08 | 亨茨曼国际有限公司 | The method for improving the fracture toughness of the reaction product comprising poly-isocyanurate |
Non-Patent Citations (1)
| Title |
|---|
| SANDRINE TEA.ET AL: "Polymeric Nanoparticles for the modification of Polyurethane Coatings", 《HTTP://D-NB.INFO/1015875327/34》 * |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113943054A (en) * | 2021-10-25 | 2022-01-18 | 常熟理工学院 | Method for efficiently cleaning fluorine-containing micro-plastic in water body by using spirulina |
| CN113943054B (en) * | 2021-10-25 | 2023-09-15 | 常熟理工学院 | Method for efficiently cleaning fluorine-containing microplastic in water body by using spirulina |
| CN115466585A (en) * | 2021-12-25 | 2022-12-13 | 闽南师范大学 | Lignin-based waterborne polyurethane-acrylate wood adhesive and preparation method thereof |
| CN115466585B (en) * | 2021-12-25 | 2023-11-10 | 闽南师范大学 | Lignin-based waterborne polyurethane-acrylate wood adhesive and preparation method thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| CN110790893B (en) | 2021-12-28 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| Meng et al. | Synthesis of novel poly (phthalazinone ether sulfone ketone) s and improvement of their melt flow properties | |
| CN110790893B (en) | Method for improving toughness and flame retardant property of polyisocyanurate | |
| CN101848956A (en) | Aromatic polyether sulfone having hydroxyphenyl end group and method for producing the same | |
| US20070117908A1 (en) | Blend for improving the brittleness and cold flowability of a carbon dioxide-propylene oxide copolymer and method for producing the same | |
| CN111019126B (en) | Polyester amide and preparation method thereof | |
| WO2019011244A1 (en) | Method for preparing high-strength and high-toughness thermosetting resin-based composite material and application thereof | |
| CN104371082B (en) | A kind of preparation method of polylactic acid composition | |
| WO2017082710A1 (en) | Method for producing wholly aromatic polyester resin with improved flowability, and wholly aromatic polyester produced thereby | |
| CN101225169B (en) | Sulfur fluoro self-crosslinkable polyimide material and preparation method thereof | |
| WO2005054366A1 (en) | Poly(3-hydroxyalkanoate) composition and molded object thereof | |
| Inoue et al. | Depression of glass transition temperature in aramid-polybutadiene multiblock copolymers | |
| CN107057047B (en) | The brush polymer of method and preparation based on poly- (N- heterocycle carbine) structure self-catalysis self-initiating open loop synthesis brush polymer | |
| CN110204723B (en) | Preparation method of heat-resistant polyphenylene sulfide | |
| CN104817697B (en) | A kind of branched polyphenylene sulfide copolymer and preparation method thereof containing condensed-nuclei aromatics | |
| JPH05132549A (en) | New biodegradable polymer and composition compounded with the same | |
| CN111454548A (en) | PHBV/HBP-C L s blend and preparation method thereof | |
| Dave et al. | Blends, Interpenetrating Polymer Networks, and Gels of Unsaturated Polyester Resin Polymers With Other Polymers | |
| CN111087652A (en) | Silicone rubber heat-resistant additive and preparation method thereof | |
| CN107973878B (en) | Copolymer, preparation method and application thereof, and blending material | |
| CN115677990B (en) | Biodegradable aromatic-aliphatic polyester copolymer and preparation method thereof | |
| Liu et al. | Synthesis and properties of high performance thermoplastic polycarbonate polyurethane elastomers through a non-isocyanate route | |
| Qiu et al. | Synthesis of poly (lactic acid)-based macro-porous foams with thermo-active shape memory property via W/O high internal phase emulsion polymerization | |
| CN108440926B (en) | High-performance stereo composite polylactic acid/elastomer alloy material or product and preparation method thereof | |
| CN116515094B (en) | Preparation method of flame-retardant degradable polyester and degradable copolymerized flame retardant | |
| CN115057999A (en) | High-heat-resistance poly (butylene succinate) composition and preparation method thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |