CN106893306A - A kind of polyurethane 3D printing material of low melting point and preparation method thereof - Google Patents
A kind of polyurethane 3D printing material of low melting point and preparation method thereof Download PDFInfo
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- CN106893306A CN106893306A CN201710046449.5A CN201710046449A CN106893306A CN 106893306 A CN106893306 A CN 106893306A CN 201710046449 A CN201710046449 A CN 201710046449A CN 106893306 A CN106893306 A CN 106893306A
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- 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
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B33—ADDITIVE MANUFACTURING TECHNOLOGY
- B33Y—ADDITIVE MANUFACTURING, i.e. MANUFACTURING OF THREE-DIMENSIONAL [3-D] OBJECTS BY ADDITIVE DEPOSITION, ADDITIVE AGGLOMERATION OR ADDITIVE LAYERING, e.g. BY 3-D PRINTING, STEREOLITHOGRAPHY OR SELECTIVE LASER SINTERING
- B33Y70/00—Materials specially adapted for additive manufacturing
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—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
- C08G18/4244—Polycondensates having carboxylic or carbonic ester groups in the main chain containing oxygen in the form of ether groups
- C08G18/4247—Polycondensates having carboxylic or carbonic ester groups in the main chain containing oxygen in the form of ether groups derived from polyols containing at least one ether group and polycarboxylic acids
- C08G18/425—Polycondensates having carboxylic or carbonic ester groups in the main chain containing oxygen in the form of ether groups derived from polyols containing at least one ether group and polycarboxylic acids the polyols containing one or two ether 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
- C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
- C08G18/72—Polyisocyanates or polyisothiocyanates
- C08G18/721—Two or more polyisocyanates not provided for in one single group C08G18/73 - C08G18/80
- C08G18/725—Combination of polyisocyanates of C08G18/78 with other polyisocyanates
-
- 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
- C08G18/77—Polyisocyanates or polyisothiocyanates having heteroatoms in addition to the isocyanate or isothiocyanate nitrogen and oxygen or sulfur
- C08G18/78—Nitrogen
- C08G18/7875—Nitrogen containing heterocyclic rings having at least one nitrogen atom in the ring
- C08G18/7881—Nitrogen containing heterocyclic rings having at least one nitrogen atom in the ring having one nitrogen atom in the ring
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- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Manufacturing & Machinery (AREA)
- Materials Engineering (AREA)
- Polyurethanes Or Polyureas (AREA)
Abstract
Polyurethane 3D printing material the invention discloses a kind of low melting point and preparation method thereof, is characterized in that component raw material and proportioning (molfraction) are：80 150 parts of the polyalcohol containing furan nucleus, 80 120 parts of diisocyanate, end group are 1 20 parts of diisocyanate compositions, 0.1 5 parts of the dendritic of maleimide.Contain dynamic chemical key Diels Alder keys in the molecular structure of polyurethane material, polyurethane 3D printing material melt temp produced by the present invention is low, print procedure is smooth, free from extraneous odour, and product surface is bright and clean, dimensionally stable, be difficult to shrink.
Description
Technical field
The present invention relates to polyurethane 3D printing Material Field, and in particular to a kind of polyurethane 3D printing material of low melting point and
Its preparation method.
Background technology
RP technique is the threedimensional model that a kind of computer sets up object, and as the skill of support direct forming
Art, is the intersection of the multiple subject such as bioengineering, material processing and forming, Automated condtrol, microcomputer modelling.With tradition shaping skill
Art is compared, and significantly reduces the R＆D cycle of new product, reduces R＆D costs.Quick forming method is divided into many kinds, such as
Laser sintered, laser fusion, fusion sediment, 3D printing, three-dimensional optical soliton interaction etc..The basic functional principle of RP technique
It is to model, pile up and Quick-forming, the physical form of object is converted into three-dimensional by modeling software or spatial digitizer first
Digital three-dimensional model, is then successively piled up material using the above method, is solidified by appropriate post processing, needed into
Shape part, RP technique is widely applied in developed country.
3D printing technique is the one kind in RP technique, and its operation principle is similar to inkjet printing, i.e. RESPONSE CALCULATION
The data signal of machine, makes molten state material or binding agent in nozzle operation chamber form drop in moment, and with certain speed
Squeezed out from nozzle, be ejected on bolster model, form the shape of profile, successively jet-stacking is continued after thin layer solidification, obtained
To the molded component of high precision.3D printing technique does not need expensive laser equipment, therefore equipment price is cheap, runs and safeguards
Cost is very low, and, 3D printing technique is also simple to operate, forming speed is fast, the free of contamination feature of forming process.
Moulding material according to injection is different, and 3D printing technique can be divided into adhesive-powder 3D printing, light-cured resin 3D
Printing and melting three kinds of techniques of 3D printing.Adhesive-powder 3D printing is to spray liquid adhesive to layer of powder material, successively
Bonding shaping；Light-cured resin 3D printing is sprayed using liquid photosensitive resin, and solidified forming is carried out with ultraviolet light.Melting 3D
Macromolecular material is sent to high temperature heat source melting, then continuous extrusion molten state macromolecule by printing, successively piles up profiled member, after
Handling process is simple, and 3D Systems companies have been developed for spraying the 3D printer of thermoplastic.
The current species of polymeric material that can be used for 3D printing is less, and that has reported mainly has acrylonitrile-butadiene-benzene second
Alkene terpolymer (ABS) and PLA (PLA), wherein ABS resin have graft copolymer with elastomer as main chain and with
Resin is the two-phase heterogeneous system structure of the graft copolymer of main chain, it is had the high chemical stability of acrylonitrile, oil resistant concurrently
The combination properties such as property and case hardness, the toughness and cold resistance of butadiene, the good dielectricity of styrene, gloss and processability.
But its intensity is not high, and as molecular weight increases, processing characteristics declines；And ABS is odorous in print procedure, shaped article is easy
Shrink, the problems such as printed product dimensional stability is not good.And PLA poor mechanical properties, easily there is brittle fracture, limit its processing
Performance.So, new 3D printing functionalized polymer material is developed to making up the fast-developing of restriction 3D printing field
Short slab is significant.
Polyurethane elastomer is a kind of new organic polymer synthetic material, its excellent in abrasion resistance, ozone resistance be fabulous,
Hardness is big, intensity is high, elasticity is good, low temperature resistant, there is good oil resistant, chemical-resistant resistance and environmental resistance, and nonpoisonous and tasteless,
Therefore its market and application field constantly expand, and quickly grow.One kind is disclosed in blue green alive patent 201410425030.7
Can be used for the polyurethane material of 3D printing, the method mixes toluene di-isocyanate(TDI) with acetone, add tetraethylammonium bromide, room
Azo diisobutyl amidine hydrochloride, 3- aminopropyl trimethoxysilanes, polyurethane particles are sequentially added after temperature stirring, it is finally heated
Stirring obtains compound polyurethane material.Sichuan University discloses a kind of poly- ammonia for 3D printing in patent 201510298936.1
Ester composite and its production and use.The compound polyurethane material by 100 parts of polyurethane, inorganic filler 0.1~10
Part, 0.1~0.5 part of light stabilizer, 0.1~0.5 part of composition of antioxidant, it is 10 to obtain compound polyurethane material powder average particle size
~100 μm, with good pliability, the introducing of inorganic filler improves the 3D printing performance of polyurethane, while so that product
With excellent mechanical property, its tensile strength is up to 20.12Mpa, elongation at break up to 511.12%.Shanghai investigation of materials
Place patent 201510278792.3 disclose a kind of thermoplastic polyurethane modified composite material for FDM 3D printings and its
Preparation method, is prepared using the raw material of following components and weight portion content：Thermoplastic polyurethane 70-95, antioxidant 1-5,
Stabilisers against hydrolysis 1-5, compatilizer 1-5, lubricant 1-5, other auxiliary agents 1-10.Zibo Zhengda Energy Saving New Materials Co., Ltd. exists
Patent 201410803193.4 discloses a kind of 3D printing polyurethane material, and it is by PPG 25-80 parts, catalyst
1-4.5 parts, polyisocyanates 2-10 parts of composition；The easy plug of solid consumptive material aimed to solve the problem that, installed that inconvenient, cost is high, the later stage additional
The problems such as needing dyeing, unstable properties.Shanghai Heng An polyurethane limited company discloses in patent 201510979494.7
A kind of 3D printing thermoplastic polyurethane material and preparation method thereof, its weight portion composition by macromolecular polyol 35-75 parts, it is fluorine-containing
Polyalcohol 0-10 parts, small molecule chain extender 2-25 parts, fluorine-containing chain extender 0-7 parts, isocyanates 5-60 parts, hydrolysis stabilizer 0-8
Part, 0-10 parts of other auxiliary agents.The preparation method is introduced in thermoplastic polyurethane material fluorine element using in-situ polymerization one-step method,
Prepare a kind of 3D printing thermoplastic polyurethane material that it has fluorochemical and TPU advantages concurrently.
The melt temperature for reducing polyurethane material helps avoid the temperature of 3D printing process and too high result in polyurethane material
The thermal degradation of material, the function due to D-A keys with thermal reversion, therefore the characteristics of reacted using D-A in polyurethane molecular structure
Building D-A keys can be effectively reduced the melt temperature of polyurethane material.Sichuan University was once public in patent 201510299301.3
Open for 3D printing, the polyurethane material containing dynamic key and its production and use, its composition is by molfraction：Two is different
50~75 parts of 100 parts of cyanate, PEPA or PPG, the glycol chain extender 50 containing Diels-Alder keys~
125 parts, 0~50 part of diisocyanate trimer crosslinking agent, 50~100 parts of the glycol chain extender containing part, slaine crosslinking
0~50 part of agent, the polyurethane material of preparation has the function of selfreparing and autoadhesion.The patent is mainly characterized by using containing
The dihydroxylic alcohols of Diels-Alder keys is as chain extender or uses the dihydroxylic alcohols containing part as chain extender, forms a kind of main chain
Polyurethane 3D printing material containing D-A keys, but the polyurethane material containing Diels-Alder keys of the patent is linear structure, phase
The polyurethane of three-dimensional-structure is compared to, the mechanical property of its material is inferior many.The performance of macromolecular material is inside it
Structure and the specific reflection of molecular motion, the architectural feature of macromolecular material have a great impact to the performance of macromolecular material.
Equally, the species of D-A keys in polyurethane molecular structure, quantity, position, design feature are to the polyurethane material performance of 3D printing
Also have a very big impact, retrieve substantial amounts of patent document and the research paper published, not yet find using containing furan nucleus
Polyalcohol, build the poly- ammonia of the 3D printing of low melting point with maleimide end-sealed isocyanate composition as crosslinking agent
The report of ester material.
The content of the invention
A kind of polyurethane of low melting point is provided the invention aims to avoid polyurethane 3D printing material thermal degradation
3D printing material and preparation method thereof, is characterized in that the polyurethane material has the corresponding Diels-Alder dynamic keys of environment,
During 3D printing, when temperature rises to critical-temperature, Diels-Alder dynamic keys fracture solution crosslinking, system viscosity is rapid
Reduce, making the melt temperature of polyurethane material reduces, be conducive to extrusion to print；When the temperature decreases, Diels-Alder dynamic keys
Re-form, be crosslinked system, enhance the mechanical property of product.
The purpose of the present invention can be achieved through the following technical solutions：
The polyurethane 3D printing material of a kind of low melting point, using following components and material rate, wherein the raw material number
Unless otherwise specified, it is molfraction；
Component raw material and proportioning：
Wherein contain molfraction >=1 of the molfraction/diisocyanate of the polyalcohol of furan nucleus.
A kind of preparation method of the polyurethane 3D printing material of low melting point, comprises the following steps：
Weigh polyalcohol 80-150 parts containing furan nucleus, diisocyanate 80-120 parts, two that end group is maleimide
Isocyanate composition 1-20 parts, dendritic 0.1-5 parts, dehydration 2-4h is melted under the conditions of being respectively placed in 30-150 DEG C
Afterwards；Reacted in addition double screw rod extruder simultaneously, polyurethane particles are obtained through underwater cutpellet, by gained polyurethane
Grain is placed in 60-200 DEG C of baking oven dries, curing 4-72h, obtains required polyurethane 3D printing material.Control screw extruder
Each section of temperature is respectively：90-120 DEG C, 120-140 DEG C, 140-150 DEG C, 150-160 DEG C, 160-180 DEG C, 90-120 DEG C.
The isocyanates be methyl diphenylene diisocyanate, toluene di-isocyanate(TDI), isofoer diisocyanate,
Hexamethylene diisocyanate, 1,5- naphthalene diisocyanates, PPDI, dimethyl diphenyl diisocyanate, hexa-methylene two
The combination of one or more of isocyanates；
The composition and preparation method containing furans cyclopolyol are：100 parts of Dicarboxylic Acids, dihydroxylic alcohols 50-100
Part, 5-50 parts of 2,5- dihydroxymethyl furans, titanate catalyst 0-1 parts add and melt in reactor, be passed through nitrogen, 170~
5-72h is reacted at 230 DEG C, 0.5mgKOH/g is less than to acid number, obtain cyclopolyol containing furans.
The end group is that the composition and preparation method of the diisocyanate compositions of maleimide are：In N2 protections and machine
Under tool stirring condition, by diisocyanate, 100 parts and organic solvent 100-200 parts are sufficiently mixed, and 200-210 is added under ice-water bath
The N- hydroxyethylmaleimides of part, add in 30 minutes, and ice-water bath continues to react 0.5-1h at room temperature after reacting 2 hours,
Then boil off organic solvent and obtain final product the diisocyanate compositions that maleimide is contained at two ends.Described organic solvent is diformazan
Base formamide, ethyl acetate, tetrahydrofuran, absolute ether, petroleum ether, toluene, acetone, dichloromethane, chloroform, dimethyl are sub-
One or more combination in sulfone, dioxane or n-hexane.
The present invention has advantages below：
The present invention improves processing fluidity, the polyurethane 3D printing material melt temp of manufacture using dendritic
Low, print procedure is smooth, free from extraneous odour, and product surface is bright and clean, dimensionally stable, is difficult to shrink.
Specific embodiment
The present invention is specifically described below by embodiment, it is necessary to which this is pointed out that the present embodiment is served only for again
To further illustrating that the present invention is carried out, it is impossible to be interpreted as limiting the scope of the invention, person skilled in art can
Some nonessential modifications and adaptations are made with according to the content of foregoing invention.Molar part is without the following number of specified otherwise
Number.
Embodiment 1：
(1) containing the preparation of furans cyclopolyol：
100 parts of adipic acid, 50 parts of 1,4- butanediols, 50 parts of 2,5- dihydroxymethyls furans, 0.5 part of titanate catalyst are added
Enter melting in reactor, be passed through nitrogen, 24-30h is reacted at 170~230 DEG C, 0.5mgKOH/g is less than to acid number, contained
Furans cyclopolyol.
(2) end group is the preparation of the diisocyanate compositions of maleimide：
Under N2 protections and mechanical agitation, by 100 parts of 100 parts of toluene di-isocyanate(TDI) and dimethylformamide fully
Mixing, adds 200 parts of N- hydroxyethylmaleimides under ice-water bath, added in 30 minutes, ice-water bath react 2 hours after in room
Temperature is lower to be continued to react 0.5-1h, is then boiled off dimethylformamide and is obtained final product the diisocyanate combination for containing maleimide in two ends
Thing.
(3) preparation of the polyurethane 3D printing material of low melting point
Weigh two isocyanides that 112 parts of cyclopolyol containing furans, 110 parts of toluene di-isocyanate(TDI), end group are maleimide
20 parts of acid ester composite, 3 parts of dendritic, after dehydration 2-4h is melted under the conditions of being respectively placed in 120 DEG C；Add simultaneously double
Reacted in spiro rod reaction extruder, polyurethane particles are obtained through underwater cutpellet, gained polyurethane particles are placed in 80 DEG C of bakings
Dried in case, cure 40h, the polyurethane 3D printing each section of temperature of control of material screw extruder needed for obtaining is respectively：90-
120 DEG C, 120-140 DEG C, 140-150 DEG C, 150-160 DEG C, 160-180 DEG C, 90-120 DEG C.After tested, the mechanics of wire rod is printed
Performance is：Tensile strength 50Mpa, bending strength 95Mpa, bending modulus 3000Mpa, elongation at break 18%.
Embodiment 2：
(1) containing the preparation of furans cyclopolyol：
100 parts of adipic acid, 80 parts of 1,4- butanediols, 21 parts of 2,5- dihydroxymethyls furans, 0.8 part of titanate catalyst are added
Enter melting in reactor, be passed through nitrogen, 35-40h is reacted at 220-230 DEG C, 0.5mgKOH/g is less than to acid number, obtain containing furan
Mutter cyclopolyol.
(2) preparation of the diisocyanate compositions of maleimide is contained at two ends：
Under N2 protections and mechanical agitation, by 150 parts of 50 parts of hexamethylene diisocyanate and dimethylformamide
It is sufficiently mixed, 100 parts of N- hydroxyethylmaleimides is added under ice-water bath, is added in 30 minutes, after ice-water bath reacts 2 hours
Continue to react 0.5-1h at room temperature, then boil off dimethylformamide and obtain final product the diisocyanate that maleimide is contained at two ends
Composition.
(3) preparation of the polyurethane 3D printing material of low melting point
It is maleimide to weigh 130 parts of the polyalcohol containing furan nucleus, 129 parts of hexamethylene diisocyanate, end group
10 parts of diisocyanate, 3 parts of dendritic, after dehydration 3h is melted under the conditions of being respectively placed in 120-150 DEG C；Add simultaneously
Reacted in double screw rod extruder, polyurethane particles are obtained through underwater cutpellet, gained polyurethane particles are placed in 60-
Dried in 200 DEG C of baking ovens, cure 24h, obtain required polyurethane 3D printing material..Control screw extruder each section of temperature point
It is not：90-120 DEG C, 120-140 DEG C, 140-150 DEG C, 150-160 DEG C, 160-180 DEG C, 90-120 DEG C.After tested, print wire
The mechanical property of material is：Tensile strength 74Mpa, bending strength 82Mpa, bending modulus 2750Mpa, elongation at break 23%.
Claims (5)
1. the polyurethane 3D printing material of a kind of low melting point, it is characterised in that following components and material rate are used, wherein described
Raw material number unless otherwise specified, is molfraction；
Component raw material and proportioning：
Wherein contain molfraction >=1 of the molfraction/diisocyanate of the polyalcohol of furan nucleus.
2. the preparation method of the polyurethane 3D printing material of a kind of low melting point, it is characterised in that comprise the following steps：
Weigh polyalcohol 80-150 parts containing furan nucleus, diisocyanate 80-120 parts, two ends contain the two different of maleimide
Cyanate compositions 1-20 parts, dendritic 0.1-5 parts, dehydration 2-4h is melted under the conditions of being respectively placed in 30-150 DEG C
Afterwards；Reacted in addition double screw rod extruder simultaneously, polyurethane particles are obtained through underwater cutpellet, by gained polyurethane
Grain is placed in 60-200 DEG C of baking oven dries, curing 4-72h, obtains required polyurethane 3D printing material.Control screw extruder
Each section of temperature is respectively：90-120 DEG C, 120-140 DEG C, 140-150 DEG C, 150-160 DEG C, 160-180 DEG C, 90-120 DEG C.
3. the preparation method of the polyurethane 3D printing material of a kind of low melting point according to claim 2, it is characterized in that described
Isocyanates is methyl diphenylene diisocyanate, toluene di-isocyanate(TDI), isofoer diisocyanate, oneself two isocyanic acids
Ester, 1,5- naphthalene diisocyanates, PPDI, dimethyl diphenyl diisocyanate, hexamethylene diisocyanate
One or more of combination.
4. the preparation method of the polyurethane 3D printing material of a kind of low melting point according to claim 2, it is characterized in that described
Composition and preparation method containing furans cyclopolyol are：100 parts of Dicarboxylic Acids, dihydroxylic alcohols 50-100 parts, 2,5- dihydroxies
Methylfuran 5-50 parts, titanate catalyst 0-1 parts adds melting in reactor, is passed through nitrogen, is reacted at 170~230 DEG C
5-72h, 0.5mgKOH/g is less than to acid number, obtains the polyalcohol containing furan nucleus.
5. the preparation method of the polyurethane 3D printing material of a kind of low melting point according to claim 2, it is characterized in that described
The two ends containing maleimide diisocyanate compositions composition and preparation method be：In N2 protections and mechanical agitation bar
Under part, by diisocyanate, 100 parts and organic solvent 100-200 parts are sufficiently mixed, and 200-210 parts of N- hydroxyls are added under ice-water bath
Ethyl maleimide, adds in 30 minutes, and ice-water bath continues to react 0.5-1h at room temperature after reacting 2 hours, then boils off
Organic solvent obtains final product the diisocyanate compositions that maleimide is contained at two ends.Described organic solvent is dimethyl formyl
Amine, ethyl acetate, tetrahydrofuran, absolute ether, petroleum ether, toluene, acetone, dichloromethane, chloroform, dimethyl sulfoxide (DMSO), dioxy
One or more combination in six rings or n-hexane.
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| CN110561754A (en) * | 2019-10-15 | 2019-12-13 | 常州增材制造研究院有限公司 | 3D printing TPU powder preparation process |
| CN111607064A (en) * | 2020-04-14 | 2020-09-01 | 南阳师范学院 | Light/heat synergistic repair type waterborne polyurethane coating material and preparation method thereof |
| CN111607064B (en) * | 2020-04-14 | 2022-04-08 | 南阳师范学院 | Light/heat synergistic repair type waterborne polyurethane coating material and preparation method thereof |
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| CN106893306B (en) | 2019-10-08 |
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