CN108456291A - A kind of shape memory type energy-absorbing protection moisture-penetrating composite material and preparation method thereof - Google Patents

A kind of shape memory type energy-absorbing protection moisture-penetrating composite material and preparation method thereof Download PDF

Info

Publication number
CN108456291A
CN108456291A CN201810066609.7A CN201810066609A CN108456291A CN 108456291 A CN108456291 A CN 108456291A CN 201810066609 A CN201810066609 A CN 201810066609A CN 108456291 A CN108456291 A CN 108456291A
Authority
CN
China
Prior art keywords
component
composite material
shape memory
moisture
parts
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
Application number
CN201810066609.7A
Other languages
Chinese (zh)
Other versions
CN108456291B (en
Inventor
刘世勇
盖静
戴江臻
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Chengdu Deco Li Polymer Material Co Ltd
Original Assignee
Chengdu Deco Li Polymer Material Co Ltd
Priority date (The priority date 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 date listed.)
Filing date
Publication date
Application filed by Chengdu Deco Li Polymer Material Co Ltd filed Critical Chengdu Deco Li Polymer Material Co Ltd
Priority to CN201810066609.7A priority Critical patent/CN108456291B/en
Publication of CN108456291A publication Critical patent/CN108456291A/en
Application granted granted Critical
Publication of CN108456291B publication Critical patent/CN108456291B/en
Active legal-status Critical Current
Anticipated expiration legal-status Critical

Links

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
    • C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
    • C08G77/04—Polysiloxanes
    • C08G77/38—Polysiloxanes modified by chemical after-treatment
    • C08G77/382—Polysiloxanes modified by chemical after-treatment containing atoms other than carbon, hydrogen, oxygen or silicon
    • C08G77/398—Polysiloxanes modified by chemical after-treatment containing atoms other than carbon, hydrogen, oxygen or silicon containing boron or metal atoms
    • 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
    • C08G18/0804—Manufacture of polymers containing ionic or ionogenic groups
    • C08G18/0819—Manufacture of polymers containing ionic or ionogenic groups containing anionic or anionogenic groups
    • C08G18/0823—Manufacture of polymers containing ionic or ionogenic groups containing anionic or anionogenic groups containing carboxylate salt groups or groups forming them
    • 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
    • C08G18/30—Low-molecular-weight compounds
    • C08G18/32—Polyhydroxy compounds; Polyamines; Hydroxyamines
    • C08G18/3203—Polyhydroxy compounds
    • C08G18/3206—Polyhydroxy compounds aliphatic
    • 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
    • C08G18/30—Low-molecular-weight compounds
    • C08G18/32—Polyhydroxy compounds; Polyamines; Hydroxyamines
    • C08G18/3203—Polyhydroxy compounds
    • C08G18/3212—Polyhydroxy compounds containing cycloaliphatic groups
    • 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
    • C08G18/30—Low-molecular-weight compounds
    • C08G18/32—Polyhydroxy compounds; Polyamines; Hydroxyamines
    • C08G18/3225—Polyamines
    • C08G18/3228—Polyamines acyclic
    • 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
    • C08G18/30—Low-molecular-weight compounds
    • C08G18/32—Polyhydroxy compounds; Polyamines; Hydroxyamines
    • C08G18/3225—Polyamines
    • C08G18/3234—Polyamines cycloaliphatic
    • 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
    • C08G18/30—Low-molecular-weight compounds
    • C08G18/34—Carboxylic acids; Esters thereof with monohydroxyl compounds
    • C08G18/348—Hydroxycarboxylic acids
    • 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
    • C08G18/4018—Mixtures of compounds of group C08G18/42 with compounds of group C08G18/48
    • 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
    • C08G18/4266—Polycondensates having carboxylic or carbonic ester groups in the main chain prepared from hydroxycarboxylic acids and/or lactones
    • C08G18/4269—Lactones
    • C08G18/4277—Caprolactone and/or substituted caprolactone
    • 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
    • C08G18/50—Polyethers having heteroatoms other than oxygen
    • C08G18/5072—Polyethers having heteroatoms other than oxygen containing sulfur
    • 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
    • C08G18/6603—Compounds of groups C08G18/42, C08G18/48, or C08G18/52 with compounds of group C08G18/32 or polyamines of C08G18/38
    • C08G18/6614—Compounds of groups C08G18/42, C08G18/48, or C08G18/52 with compounds of group C08G18/32 or polyamines of C08G18/38 with compounds of group C08G18/3225 or C08G18/3271 and/or polyamines of C08G18/38
    • C08G18/6618—Compounds of groups C08G18/42, C08G18/48, or C08G18/52 with compounds of group C08G18/32 or polyamines of C08G18/38 with compounds of group C08G18/3225 or C08G18/3271 and/or polyamines of C08G18/38 with compounds of group C08G18/3225 or polyamines of C08G18/38
    • 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
    • C08G18/6659—Compounds of group C08G18/42 with compounds of group C08G18/34
    • 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
    • C08G18/73—Polyisocyanates or polyisothiocyanates acyclic
    • 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
    • C08G18/75—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic
    • C08G18/751—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic containing only one cycloaliphatic ring
    • C08G18/752—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic containing only one cycloaliphatic ring containing at least one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group
    • C08G18/753—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic containing only one cycloaliphatic ring containing at least one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group containing one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group having a primary carbon atom next to the isocyanate or isothiocyanate group
    • C08G18/755—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic containing only one cycloaliphatic ring containing at least one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group containing one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group having a primary carbon atom next to the isocyanate or isothiocyanate group and at least one isocyanate or isothiocyanate group linked to a secondary carbon atom of the cycloaliphatic ring, e.g. isophorone diisocyanate
    • 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
    • C08G18/7614—Polyisocyanates or polyisothiocyanates cyclic aromatic containing only one aromatic ring
    • 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
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L75/00—Compositions of polyureas or polyurethanes; Compositions of derivatives of such polymers
    • C08L75/04—Polyurethanes
    • C08L75/06—Polyurethanes from polyesters
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L83/00—Compositions of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon only; Compositions of derivatives of such polymers
    • C08L83/04—Polysiloxanes
    • C08L83/08—Polysiloxanes containing silicon bound to organic groups containing atoms other than carbon, hydrogen and oxygen
    • 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
    • C08G2280/00—Compositions for creating shape memory
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2201/00—Properties
    • C08L2201/12—Shape memory

Abstract

The invention discloses a kind of shape memory type energy-absorbings, and moisture-penetrating composite material and preparation method thereof, the shape memory energy-absorbing protection moisture-penetrating composite material to be protected to be made of the two kinds of material mixings of component A and B component, and the weight ratio of component A and B component is 5 500:100；Wherein, component A is the polyurethane resin with moisture-inhibiting and shape memory function, and B component is the boron modification organic siliconresin with shear thickening function.In the present invention, component A can provide support for composite material, help composite molding, moisture-inhibiting, and restore its original shape by heating after composite material deformation, B component can be hardened when being violently shaken with energy-absorbing, provide composite material excellent barrier propterty.

Description

A kind of shape memory type energy-absorbing protection moisture-penetrating composite material and preparation method thereof
Technical field
The invention belongs to field of polymer composite material, be related to a kind of shape memory type energy-absorbing protection moisture-penetrating composite material and Preparation method.
Background technology
Shear thickening materials maximum feature be when the strain rate of extraneous stress be more than critical shear rate when, viscosity of material Or modulus becomes larger rapidly, is changed into hard solid state rapidly by limp state, to play the role of energy-absorbing protection.Shear thickening materials Include mainly two major classes, one is the particle,colloid being made of nano particle and liquid dispersion medium, another kind is with boron modification Organic siliconresin is the molecular colloid of representative.It is shellproof that the patent of 101871748 A of Publication No. CN discloses a kind of soft stab-proof Material, the material provide its energy-absorbing protection effect using particle,colloid, but particle,colloid can not plastotype, it usually needs seal It uses, and nano particle therein can gradually reunite sedimentation, to lose protective action, and molecular colloid is without sealing, property It can stablize, more and more concerns gradually be obtained, such as Publication No. CN 104862975B, CN 102037088A, CN The shear thickening materials of the patent disclosures such as 102926211B are such.Although molecular colloid can be with plastotype, its constancy is poor, Smaller stress can lead to its deformation, so aforementioned patent, which is inclined to, uses it for dipping fabric, this solves material flexible type The problem of, but the application range of the material is limited, and boron modification organic siliconresin penetrability is poor, is used for after impregnating fabric Human body unfavorable moisture-inhibiting when dressing, reduces snugness of fit.In addition, although shear thickening materials and part high-performance textile are shellproof Effect is preferable, but its anti-stab effect is poor, still there is shortcoming in barrier propterty.
Invention content
It is an object of the invention to overcome the deficiencies of the prior art and provide a kind of protection moisture-inhibiting of shape memory type energy-absorbing is compound Material and preparation method thereof, by a large amount of hydrophilic radicals introducing polyurethane resin to provide good penetrability for composite material, Make polyurethane resin that there is temperature control shape memory function by MOLECULE DESIGN, to which composite material plastotype can be helped to shape, again Composite material can be helped to restore original shape by heating after blastic deformation, and inhaled not influencing boron modification organic siliconresin Under the premise of energy protection effect, certain anti-stab effect is provided for composite material.
The purpose of the present invention is achieved through the following technical solutions：A kind of shape memory type energy-absorbing protection moisture-inhibiting is compound The weight ratio of material, including component A and B component, the component A and B component is 5-500 ︰ 100；
The component A is the polyurethane resin with moisture-inhibiting and shape memory function；
The B component is the boron modification organic siliconresin with shear thickening function.
Preferably, the weight ratio of the component A and B component is 30-200:100.
A kind of preparation method of shape memory type energy-absorbing protection moisture-penetrating composite material, the energy-absorbing protect moisture-penetrating composite material It is kneaded and is made by component A and B component；
The weight ratio of the component A and B component is 5-500 ︰ 100, and the component A is with moisture-inhibiting and shape memory function Polyurethane resin, the B component are the boron modification organic siliconresin with shear thickening function.
Preferably, the weight ratio of the component A and B component is 30-200:100.
Preferably, the preparation of the component A includes the following steps, wherein raw materials used in terms of mass fraction：
100 parts of the poly-dihydric alcohol that relative molecular mass is 2000-6000 is added in sealing Scattered Kettle, diisocyanate is sequentially added 8-40 parts of ester, 0-0.1 parts of catalyst, 0.5-5 parts of small molecule chain extender, 10-15 parts of hydrophilic chain extender react 4-6 hours, temperature Then degree control is cooled to 30 DEG C at 70-90 DEG C, 0-12 parts of neutralizations of neutralizer are added, deionized water stirring and emulsifying are added, then 0.5-5 parts of rear chain extenders are added, the aqueous polyurethane emulsion that solid content is 20% -30% is made；
The aqueous polyurethane emulsion is spray-dried to get component A.
Preferably, the poly-dihydric alcohol includes polycarbonate glycol, polycaprolactone diols and polyadipate binary alcohol esters two At least one of first alcohol；
The diisocyanate includes that toluene di-isocyanate(TDI), methyl diphenylene diisocyanate, hydrogenated diphenyl methane two are different At least one of cyanate, isoflurane chalcone diisocyanate, hexamethylene diisocyanate；
The catalyst includes at least one of organic bismuth catalyst and organic silver catalyst；
The small molecule chain extender include in 1,4-butanediol, Isosorbide-5-Nitrae-cyclohexane dimethanol, ethylene glycol, 1,6- hexylene glycols at least It is a kind of；
The hydrophilic chain extender includes 2,2- dihydromethyl propionic acids, 2- (2- amino-ethyls) tarine sodium salt, α, ω-poly- third At least one of glycol-diamines-sulfopropyl sodium salt；
The neutralizer includes at least one of triethylamine, dimethylethanolamine, 2-amino-2-methyl-1-propanol；
The rear chain extender includes at least one of ethylenediamine, hexamethylene diamine, methyl cyclohexane diamines, hydrazine hydrate.
Preferably, the sealing Scattered Kettle is the sealing Scattered Kettle with temperature control and dispersal device.
Preferably, the preparation of the B component includes the following steps, wherein raw materials used in terms of mass fraction：
100 parts of polysiloxanes is taken, 5-20 parts of boride is added thereto, control temperature is at 120-300 DEG C, after reacting 2-6 hours Up to B component.
Preferably, the polysiloxanes is the dimethyl silicone polymer at least provided with two silanol functionals.
Preferably, the boride is at least one of boric acid, boron oxide, pyroboric acid.
The beneficial effects of the invention are as follows：
（1）Energy-absorbing provided by the invention with shape memory function protects moisture-penetrating composite material with the shape with hydrophilic radical Raw material based on memory polyurethane resin and boron modification organic siliconresin, the introducing of hydrophilic radical assign composite material certain saturating Wet performance improves comfort when it is used for human body wearing material；
（2）Shape memory polyurethane material used in the present invention has good plastotype and constancy, polyurethane material when heating Can random plastotype, can shape after cooling, to the composite material strong applicability, have a wide range of application, can be used for external fixation of fracture The civil uses such as material, sport protection material, automobile-used anticollision material can also coordinate high-performance fiber etc. for flak jackets, prevent The military purposes such as bullet helmet；
（3）Shape memory polyurethane material used in the present invention has excellent intensity and toughness at room temperature, is used for protective materials When certain anti-stab effect can be provided；
（4）Boron modification silicone resin material used in the present invention has excellent energy-absorbing effect, when by quick washing at once It is hardened, to provide composite material good protection effect；
（5）Shape memory polyurethane provided by the invention can restore its original-shape after heat temperature raising again, therefore assign Composite material recoverability certain when impaired, and the composite material can be iteratively repeated utilization, after complete breakage still Can mixing and molding again, avoid the waste of resource and the pollution of environment destroyed.
Specific implementation mode
Below in conjunction with embodiment, technical scheme of the present invention is clearly and completely described, it is clear that described Embodiment is only a part of the embodiment of the present invention, instead of all the embodiments.Based on the embodiments of the present invention, this field The every other embodiment that technical staff is obtained under the premise of not making the creative labor belongs to what the present invention protected Range.
Embodiment 1
A kind of shape memory type energy-absorbing protection moisture-penetrating composite material is present embodiments provided, the composite material is by component A and B Component is kneaded and obtains, and wherein component A is 50 parts of polyurethane resins, and B component is 100 parts of boron modification silicone resin materials.
Above-mentioned component A polyurethane resin passes through following step and prepares successively：
The sealing with heating, temperature control and dispersal device is added in 100 parts of the polycaprolactone diols that relative molecular mass is 6000 In Scattered Kettle, 8 parts of hexamethylene diisocyanate is added, 0.1 part of organic silver catalyst is reacted 2 hours in 90 degree, is then added 0.5 part of Isosorbide-5-Nitrae-cyclohexane dimethanol reacts 1 hour, and hydrophilic chain extender α, ω-polypropylene glycol-diamines-sulfopropyl sodium salt 10 is added Part reaction 1 hour, is cooled to 30 DEG C, and the emulsification of deionized water high-speed stirred is added, and 0.5 part of ethylenediamine is then added, obtained to contain admittedly The aqueous polyurethane emulsion that amount is 20%；
Above-mentioned aqueous polyurethane emulsion is spray-dried to get the polyurethane resin with moisture-inhibiting and shape memory function.
Above-mentioned B component boron modification organic siliconresin is prepared by following step：
Take 100 parts of dialkyl polydimethylsiloxanes（Niu Boli Chemical Co., Ltd.s, trade mark NEWTECH-1381）, boron is added 5 parts of acid, reacts 2 hours to get B component boron modification organic siliconresin at 300 DEG C.
Composite material provided in this embodiment has excellent energy-absorbing protection effect, and has certain shape memory work( Can, the introducing of sodium group also assigns composite material good penetrability.
Embodiment 2
A kind of shape memory type energy-absorbing protection moisture-penetrating composite material is present embodiments provided, the composite material is by component A and B Component is kneaded and obtains, and wherein component A is 5 parts of polyurethane resins, and B component is 100 parts of boron modification silicone resin materials.
Above-mentioned component A polyurethane resin passes through following step and prepares successively：
The sealing with heating, temperature control and dispersal device is added in 100 parts of the polycarbonate glycol that relative molecular mass is 2000 In Scattered Kettle, 40 parts of toluene di-isocyanate(TDI) is added, is reacted 2 hours in 70 degree, it is small that 1,6- hexylene glycols, 5 parts of reactions 1 are then added When, hydrophilic chain extender 2 is added, 13 parts of 2- dihydromethyl propionic acids react 3 hours, are cooled to 30 DEG C, and 10 parts of progress of triethylamine are added It neutralizes, the emulsification of deionized water high-speed stirred is added after neutralizing completely, 5 parts of methyl cyclohexane diamines are then added, obtained solid content is 30% aqueous polyurethane emulsion；
Above-mentioned aqueous polyurethane emulsion is spray-dried to get the polyurethane resin with moisture-inhibiting and shape memory function.
Above-mentioned B component boron modification organic siliconresin is prepared by following step：
Take 100 parts of dialkyl polydimethylsiloxanes（Niu Boli Chemical Co., Ltd.s, trade mark NEWTECH-1384）, it is added burnt 20 parts of boric acid reacts 6 hours to get B component boron modification organic siliconresin at 160 DEG C.
Embodiment 3
A kind of shape memory type energy-absorbing protection moisture-penetrating composite material is present embodiments provided, the composite material is by component A and B Component is kneaded and obtains, and wherein component A is 200 parts of polyurethane resins, and B component is 100 parts of boron modification silicone resin materials.
Above-mentioned component A polyurethane resin passes through following step and prepares successively：
Band heating, temperature control and dispersion dress is added in 100 parts of the polyadipate binary alcohol esters dihydric alcohol that relative molecular mass is 3000 In the sealing Scattered Kettle set, 38 parts of isoflurane chalcone diisocyanate is added, organic bismuth catalyst is 0.07 part small in 85 degree of reactions 2 When, 1 part of 1,4-butanediol is then added and reacts 0.5 hour, hydrophilic chain extender 2 is added, the 15 parts of reactions 3 of 2- dihydromethyl propionic acids are small When, 30 DEG C are cooled to, 12 parts of triethylamine is added and is neutralized, the emulsification of deionized water high-speed stirred is added after neutralizing completely, then 1 part of hexamethylene diamine is added, the aqueous polyurethane emulsion that solid content is 30% is made；
Above-mentioned aqueous polyurethane emulsion is spray-dried to get the polyurethane resin with moisture-inhibiting and shape memory function.
Above-mentioned B component boron modification organic siliconresin is prepared by following step：
Take 100 parts of dialkyl polydimethylsiloxanes（Niu Boli Chemical Co., Ltd.s, trade mark NEWTECH-1385）, boron is added 10 parts of acid, reacts 5 hours to get B component boron modification organic siliconresin at 140 DEG C.
Embodiment 4
A kind of shape memory type energy-absorbing protection moisture-penetrating composite material is present embodiments provided, the composite material is by component A and B Component is kneaded and obtains, and wherein component A is 500 parts of polyurethane resins, and B component is 100 parts of boron modification silicone resin materials.
Above-mentioned component A polyurethane resin passes through following step and prepares successively：
The sealing with heating, temperature control and dispersal device is added in 100 parts of the polycaprolactone diols that relative molecular mass is 4000 In Scattered Kettle, it is added 35 parts of methyl diphenylene diisocyanate, 0.03 part of organic bismuth catalyst was in 60 degree reactions 2 hours, then 0.6 part of 1,4-butanediol is added to react 0.5 hour, hydrophilic chain extender 2 is added, 11 parts of 2- dihydromethyl propionic acids react 3 hours, drop Temperature is added 9 parts of triethylamine and is neutralized to 30 DEG C, and the emulsification of deionized water high-speed stirred is added after neutralizing completely, is then added 1.2 Part hydrazine hydrate（80% aqueous solution）, the aqueous polyurethane emulsion that solid content is 25% is made；
Above-mentioned aqueous polyurethane emulsion is spray-dried to get the polyurethane resin with moisture-inhibiting and shape memory function.
Above-mentioned B component boron modification organic siliconresin is prepared by following step：
Take 100 parts of dialkyl polydimethylsiloxanes（Niu Boli Chemical Co., Ltd.s, trade mark NEWTECH-1385）, boron is added 8 parts of acid, reacts 4 hours to get B component boron modification organic siliconresin at 120 DEG C.
The above is only a preferred embodiment of the present invention, it should be understood that the present invention is not limited to described herein Form is not to be taken as excluding other embodiments, and can be used for other combinations, modifications, and environments, and can be at this In the text contemplated scope, modifications can be made through the above teachings or related fields of technology or knowledge.And those skilled in the art institute into Capable modifications and changes do not depart from the spirit and scope of the present invention, then all should be in the protection domain of appended claims of the present invention It is interior.

Claims (10)

1. a kind of shape memory type energy-absorbing protects moisture-penetrating composite material, which is characterized in that including component A and B component, the A groups Divide and the weight ratio of B component is 5-500 ︰ 100；
The component A is the polyurethane resin with moisture-inhibiting and shape memory function；
The B component is the boron modification organic siliconresin with shear thickening function.
2. a kind of shape memory type energy-absorbing according to claim 1 protects moisture-penetrating composite material, which is characterized in that the A The weight ratio of component and B component is 30-200:100.
3. a kind of preparation method of shape memory type energy-absorbing protection moisture-penetrating composite material, which is characterized in that the energy-absorbing protection is saturating Wet composite material is kneaded by component A and B component and is made；
The weight ratio of the component A and B component is 5-500 ︰ 100, and the component A is with moisture-inhibiting and shape memory function Polyurethane resin, the B component are the boron modification organic siliconresin with shear thickening function.
4. a kind of preparation method of shape memory type energy-absorbing protection moisture-penetrating composite material according to claim 3, feature It is, the weight ratio of the component A and B component is 30-200:100.
5. a kind of preparation method of shape memory type energy-absorbing protection moisture-penetrating composite material according to claim 3, feature It is, the preparation of the component A includes the following steps, wherein raw materials used in terms of mass fraction：
100 parts of the poly-dihydric alcohol that relative molecular mass is 2000-6000 is added in sealing Scattered Kettle, diisocyanate is sequentially added 8-40 parts of ester, 0-0.1 parts of catalyst, 0.5-5 parts of small molecule chain extender, 10-15 parts of hydrophilic chain extender react 4-6 hours, temperature Then control is cooled to 30 DEG C at 70-90 DEG C, 0-12 parts of neutralizations of neutralizer are added, deionized water stirring and emulsifying is added, then adds Enter 0.5-5 parts of rear chain extenders, the aqueous polyurethane emulsion that solid content is 20% -30% is made；
The aqueous polyurethane emulsion is spray-dried to get component A.
6. a kind of preparation method of shape memory type energy-absorbing protection moisture-penetrating composite material according to claim 5, feature It is, the poly-dihydric alcohol includes in polycarbonate glycol, polycaprolactone diols and polyadipate binary alcohol esters dihydric alcohol At least one；
The diisocyanate includes that toluene di-isocyanate(TDI), methyl diphenylene diisocyanate, hydrogenated diphenyl methane two are different At least one of cyanate, isoflurane chalcone diisocyanate, hexamethylene diisocyanate；
The catalyst includes at least one of organic bismuth catalyst and organic silver catalyst；
The small molecule chain extender include in 1,4-butanediol, Isosorbide-5-Nitrae-cyclohexane dimethanol, ethylene glycol, 1,6- hexylene glycols at least It is a kind of；
The hydrophilic chain extender includes 2,2- dihydromethyl propionic acids, 2- (2- amino-ethyls) tarine sodium salt, α, ω-poly- third At least one of glycol-diamines-sulfopropyl sodium salt；
The neutralizer includes at least one of triethylamine, dimethylethanolamine, 2-amino-2-methyl-1-propanol；
The rear chain extender includes at least one of ethylenediamine, hexamethylene diamine, methyl cyclohexane diamines, hydrazine hydrate.
7. a kind of preparation method of shape memory type energy-absorbing protection moisture-penetrating composite material according to claim 5, feature It is, the sealing Scattered Kettle is the sealing Scattered Kettle with temperature control and dispersal device.
8. a kind of preparation method of shape memory type energy-absorbing protection moisture-penetrating composite material according to claim 3, feature It is, the preparation of the B component includes the following steps, wherein raw materials used in terms of mass fraction：
100 parts of polysiloxanes is taken, 5-20 parts of boride is added thereto, control temperature is at 120-300 DEG C, after reacting 2-6 hours Up to B component.
9. a kind of preparation method of shape memory type energy-absorbing protection moisture-penetrating composite material according to claim 8, feature It is, the polysiloxanes is the dimethyl silicone polymer at least provided with two silanol functionals.
10. a kind of preparation method of shape memory type energy-absorbing protection moisture-penetrating composite material according to claim 8, feature It is, the boride is at least one of boric acid, boron oxide, pyroboric acid.
CN201810066609.7A 2018-01-24 2018-01-24 Shape memory type energy-absorbing protective moisture-permeable composite material and preparation method thereof Active CN108456291B (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN201810066609.7A CN108456291B (en) 2018-01-24 2018-01-24 Shape memory type energy-absorbing protective moisture-permeable composite material and preparation method thereof

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN201810066609.7A CN108456291B (en) 2018-01-24 2018-01-24 Shape memory type energy-absorbing protective moisture-permeable composite material and preparation method thereof

Publications (2)

Publication Number Publication Date
CN108456291A true CN108456291A (en) 2018-08-28
CN108456291B CN108456291B (en) 2020-11-17

Family

ID=63238604

Family Applications (1)

Application Number Title Priority Date Filing Date
CN201810066609.7A Active CN108456291B (en) 2018-01-24 2018-01-24 Shape memory type energy-absorbing protective moisture-permeable composite material and preparation method thereof

Country Status (1)

Country Link
CN (1) CN108456291B (en)

Cited By (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN109438666A (en) * 2018-10-31 2019-03-08 湖南御邦华安新材料科技有限公司 Low temperature resistant, anti-ballistic materials and its preparation method and application
CN110128626A (en) * 2019-04-29 2019-08-16 镇江利德尔复合材料有限公司 A kind of method that organosilicon improves polyurethane shape memory material thermal stability
CN111171494A (en) * 2018-11-12 2020-05-19 中国科学院化学研究所 Impact-resistant shear-thickening polyurethane hydrogel and preparation method thereof
CN112574569A (en) * 2019-09-30 2021-03-30 中国科学院化学研究所 Multi-temperature response shape memory organic silicon rubber material and preparation method and application thereof
CN115093709A (en) * 2022-06-29 2022-09-23 中国科学院长春应用化学研究所 Hydrolysis-resistant polyborosiloxane and preparation method thereof
CN116082598A (en) * 2022-12-14 2023-05-09 合肥安利聚氨酯新材料有限公司 Water-based polyurethane resin with impact resistance, and preparation method and application thereof

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20140147632A1 (en) * 2011-07-19 2014-05-29 Clariant International Ltd. Process For The Production Of Polyurethane Polyureas Containing Side Chains And Of Aqueous Dispersions Of These
CN104046223A (en) * 2014-07-09 2014-09-17 朱蕾 Preparation method of flame-retardant aqueous polyurethane coating
CN105273603A (en) * 2015-08-27 2016-01-27 浙江工商大学 Building facade coating and preparation method thereof

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20140147632A1 (en) * 2011-07-19 2014-05-29 Clariant International Ltd. Process For The Production Of Polyurethane Polyureas Containing Side Chains And Of Aqueous Dispersions Of These
CN104046223A (en) * 2014-07-09 2014-09-17 朱蕾 Preparation method of flame-retardant aqueous polyurethane coating
CN105273603A (en) * 2015-08-27 2016-01-27 浙江工商大学 Building facade coating and preparation method thereof

Cited By (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN109438666A (en) * 2018-10-31 2019-03-08 湖南御邦华安新材料科技有限公司 Low temperature resistant, anti-ballistic materials and its preparation method and application
CN111171494A (en) * 2018-11-12 2020-05-19 中国科学院化学研究所 Impact-resistant shear-thickening polyurethane hydrogel and preparation method thereof
CN111171494B (en) * 2018-11-12 2021-01-26 中国科学院化学研究所 Impact-resistant shear-thickening polyurethane hydrogel and preparation method thereof
CN110128626A (en) * 2019-04-29 2019-08-16 镇江利德尔复合材料有限公司 A kind of method that organosilicon improves polyurethane shape memory material thermal stability
CN112574569A (en) * 2019-09-30 2021-03-30 中国科学院化学研究所 Multi-temperature response shape memory organic silicon rubber material and preparation method and application thereof
CN112574569B (en) * 2019-09-30 2022-08-16 中国科学院化学研究所 Multi-temperature response shape memory organic silicon rubber material and preparation method and application thereof
CN115093709A (en) * 2022-06-29 2022-09-23 中国科学院长春应用化学研究所 Hydrolysis-resistant polyborosiloxane and preparation method thereof
CN116082598A (en) * 2022-12-14 2023-05-09 合肥安利聚氨酯新材料有限公司 Water-based polyurethane resin with impact resistance, and preparation method and application thereof

Also Published As

Publication number Publication date
CN108456291B (en) 2020-11-17

Similar Documents

Publication Publication Date Title
CN108456291A (en) A kind of shape memory type energy-absorbing protection moisture-penetrating composite material and preparation method thereof
Santamaria-Echart et al. Advances in waterborne polyurethane and polyurethane-urea dispersions and their eco-friendly derivatives: A review
Lu et al. Soybean-oil-based waterborne polyurethane dispersions: effects of polyol functionality and hard segment content on properties
CN107383848A (en) A kind of preparation method of aqueous polyurethane/graphene nano complex emulsions
CN105456056B (en) Facial mask hydrogel composition comprising soluble polyurethane
Wang et al. Dissolution and processing of silk fibroin for materials science
CN101230189B (en) Method for preparing polysaccharide nano-crystalline grafted polyester modified polyurethane material
CN106963980B (en) Preparation method and application of chitosan-silicon dioxide nano hybrid material
CN1648143A (en) Polyurethane with shape memory property, composition containing it and shape memory fabric prepared therefrom
CN112679690B (en) Energy-absorbing material and preparation method thereof
Khalid et al. 3D/4D printing of cellulose nanocrystals-based biomaterials: Additives for sustainable applications
CN107033563B (en) A kind of activeness and quietness poly-lactic acid material and preparation method thereof
Han et al. Recent advances in skin collagen: functionality and non-medical applications
Wu et al. Advances in antimicrobial polymer coatings in the leather industry: a comprehensive review
WO2022019179A1 (en) Rubber particles, composite particles, and production methods therefor
CN107298836A (en) A kind of graphene crystal composite polylactic acid anti-biotic material and preparation method thereof
Sbardella et al. Zinc oxide nanostructures and stearic acid as surface modifiers for flax fabrics in polylactic acid biocomposites
CN109971037A (en) Phosphorous nano-meter flame retardants and preparation method thereof
Hasan et al. Silk protein and its nanocomposites
CN101402718B (en) Process for producing material with equivalent heat-transfer performance of human body skin
Xing et al. Crosslinked chitosan‐based biocomposite films modified with soy protein isolate
Mase et al. A new silkworm race for sericin production,“SERICIN HOPE” and its product,“VIRGIN SERICIN”
CN108359143A (en) A kind of hydrogel 3D printing material and preparation method thereof
JP4940476B2 (en) An antibacterial and deodorizing agent for fibers and a fiber product processed with the agent.
CN1183161C (en) Lactide modified starch derivative and its preparation method

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