CN106008900B - A kind of polyurethane-polyesteramide compound and preparation method thereof - Google Patents
A kind of polyurethane-polyesteramide compound and preparation method thereof Download PDFInfo
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- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
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- C08G18/00—Polymeric products of isocyanates or isothiocyanates
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- 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
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- C08G18/00—Polymeric products of isocyanates or isothiocyanates
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- 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
- C08G18/6607—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 C08G18/3203
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- 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
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- C08G18/6637—Compounds of group C08G18/42 with compounds of group C08G18/32 or polyamines of C08G18/38
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- 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
- C08G18/6666—Compounds of group C08G18/48 or C08G18/52
- C08G18/667—Compounds of group C08G18/48 or C08G18/52 with compounds of group C08G18/32 or polyamines of C08G18/38
- C08G18/6674—Compounds of group C08G18/48 or C08G18/52 with compounds of group C08G18/32 or polyamines of C08G18/38 with compounds of group C08G18/3203
- C08G18/6677—Compounds of group C08G18/48 or C08G18/52 with compounds of group C08G18/32 or polyamines of C08G18/38 with compounds of group C08G18/3203 having at least three hydroxy groups
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Abstract
The present invention is a kind of polyurethane-polyesteramide compound, and the chemical structural formula of the compound is as follows.The present invention introduces cyclic carbonate during isocyanates reacts with polymer polyatomic alcohol and prepares polyurethane, and polyurethane-polyesteramide compound is prepared in situ.The compound combines the advantages that the advantages that higher modulus of polyesteramide and intensity, preferable wear-resisting and heat resistance and good elasticity of polyurethane, oil resistivity, water resistance, high resiliency, can be widely applied to the fields such as building, automobile manufacture, rag trade, household, electronics industry, medical treatment.Wherein, R1、R2、R3It is alkyl or substituted hydrocarbon radical.
Description
Technical field：
The invention belongs to technical field of polymer synthetic chemistry, provide a kind of polyurethane-polyesteramide compound and its
Preparation method.
Background technique：
Polyurethane material is a kind of high-molecular compound for repeating carbamate groups containing there are many on main chain, the material
Expect that intensity is high, hardness range is wide, and wear-resisting property is good, and has good elasticity, oil resistivity, ozone resistance, resistance to ray radiation
Property, adhesiveness, while gas transmission coefficient is small, damping capaicty is strong, cryogenic property is also very outstanding, oneself is widely used in national warp
The every field of Ji.In (Xu Peilin etc., polyurethane material handbook [M] Chemical Industry Press, 2002.) but polyurethane material
Heat is big, and high temperature resistance is general, and especially wet-hot aging performance is bad.In addition, polyurethane material is intolerant to intensive polar solvent and by force
Acid-alkali medium, such as at a certain temperature, alcohol, acid, ketone can make polyurethane elastomer be swollen and degrade, chloroform, methylene chloride, diformazan
Base formamide equal solvent will be such that polyurethane elastomer is swollen at normal temperature.(the new rubber industry of Hao Li, 1999 (5):315-
319.；Li Ting polyurethane, 2012,8:022.).Polyesteramide material is not only to contain ester group in molecule but also contain amide groups
High molecular material, which had both had many advantages, such as the good erosion-resisting characteristics of polyester material, higher modulus and intensity, had also had
The high glass transition temperature of polyamide material, higher fusing point and heat resistance and wear resistance, chemical resistance and
The advantages that self-lubrication.Therefore, can have complementary advantages between polyurethane material and polyesteramide material, in conjunction with polyurethane material and
The advantages of polyesteramide material the more outstanding material of available performance.And by the preparation process knot of polyurethane and polyesteramide
It is to realize the effective way having complementary advantages that polyurethane-polyesteramide compound is prepared in situ altogether.
Ionic polymerization technology can improve old synthetic method as one kind and prepare the effective ways of new polymers,
Compound field is prepared in situ has obtained very big concern.Imperial (the in-situ polymerization polyamide 6/reactive polymer alloy of such as company of time
Research [D] Institute of Chemistry, Academia Sinica, 2006.) Polyether-type thermoplastic polyurethane elastomer was once dissolved in acyl in oneself
In amine melt, and macromolecular activator can be formed, caprolactam polymerization is caused with Basic fluxing raction occurs in caprolactam melt
It generates copolymer and has reached nanoscale to make dispersing and disintegrating of the thermoplastic polyurethane elastomer in base polyamide.Hou
Deng (Polym.Int., 2006,55 (6):Reaction dissolvent 643-649.) is used as using epsilon-caprolactams (CL), CL- sodium is used as and urges
Agent, using the method for cationic ring opening polymerization in situ in the thermoplastic polyurethane solution dissolved with different quality containing synthetic nylon
6, so that nylon 6 and thermoplastic polyurethane blends be made.(chemical engineering and equipment, 2014 (8) such as Chen Lu justice:21-23.)
Polyester polyurethane (PES-TPU)/MC nylon 6 in-situ composite material is prepared for by caprolactam anionic ring-opening polymerization method.
The predominantly interior acyl of monomer although many by the report that compound is prepared in situ in ionic polymerization, for anionic ring-opening polymerization
Amine, the matrix of compound are mainly polyamide, be modified it by introducing polyurethane.These methods have preparation step multiple
The disadvantages of miscellaneous, raw materials used at high cost, polyamide and polyurethane only have physical bond in gained compound.In addition, these are prepared
Catalyst used in method is sodium hydroxide, and catalyst functions only as catalysis implementing anionic lactam polymerisation into the effect of polyamide.At present
There has been no polyurethane-polyesteramide compound report is prepared in situ using cyclic carbonate.Beilin etc.
(Russ.J.Appl.Chem.,2005,79(1):133-136.) discovery tertiary amine compounds can trigger cyclic carbonate with it is different
Cyanate copolymerization obtains polyesteramide analog copolymer, which can carry out under the conditions of mild temperature, but be not introduced into
Polyurethane-modified, product water imbibition is big, and dimensional stability is bad.
Summary of the invention：
The present invention is for, there are preparation step complexity, at high cost and only physical bond deficiency mentions in current techniques
A kind of polyurethane-polyesteramide compound and preparation method thereof is supplied.It is existing between polyesteramide and polyurethane in the compound
Chemical bonding has physical bond again.The preparation method of the compound is by reacting preparation with isocyanates in polymer polyatomic alcohol
Reacting for cyclic carbonate and isocyanates is introduced during polyurethane, and a kind of polyurethane-polyamide has been prepared in situ out
Ester complexes.
The technical scheme is that：
A kind of polyurethane-polyesteramide compound, the chemical structural formula of the compound are as follows：
Wherein, R1、R2、R3It is alkyl or substituted hydrocarbon radical.
The R1Specially：
The R2Specially：
The R3Specially：
The polyurethane-polyesteramide compound in-situ preparation method, includes the following steps：
(1) polymer polyatomic alcohol is spare after vaccum dewatering 3h-6h under the conditions of 90 DEG C -120 DEG C；
(2) by polymer polyatomic alcohol, cyclic carbonate and chain extender by dehydration in 40 DEG C of -80 DEG C of vacuumize processs
1h-3h；Wherein, molar ratio is polymer polyatomic alcohol：Chain extender=2.0-16.0：1；Mass ratio is cyclic carbonate：Polymer
Polyalcohol=0.1-10：10；
(3) restore normal pressure, isocyanates and tertiary amine catalyst is added, after mixing evenly, 40 DEG C of -80 DEG C of preheatings of injection
In mold, 1h-3h is reacted, then vacuumizing and defoaming；Wherein, molar ratio is isocyanates：Polymer polyatomic alcohol and cyclic carbonate
The sum of ester=0.6-1.4：1；Tertiary amine catalyst is the 0.1%-5% of the pure and mild cyclic carbonate gross mass of polymer polyol；
(4) the reaction was continued at lower 40 DEG C -80 DEG C of normal pressure 2h-6h, then 90 DEG C of -120 DEG C of solidification 12h-24h；
(5) after demoulding, polyurethane-polyesteramide compound；
The molal quantity of the isocyanates is in terms of the isocyanic acid radical that it has；
The polymer polyatomic alcohol molal quantity is in terms of the molal quantity of its hydroxyl having；
The molal quantity of the chain extender is in terms of the sum of its molal quantity of hydroxyl and amino having.
The isocyanates is aromatic isocyanate, aliphatic isocyanates or alicyclic isocyanate.Specially first
Phenylene diisocyanate, methyl diphenylene diisocyanate, paraphenylene diisocyanate, 3,3'- dimethyl -4,4'- biphenyl, two isocyanide
Acid esters, 3,3- dichloro- biphenyl 4,4- diisocyanate, hexamethylene diisocyanate, 1,5- naphthalene diisocyanate, different Fo Er
Ketone diisocyanate, 4,4- hexylmethanes, O-phthalic group diisocyanate, tri-methyl hexamethylene two
Isocyanates, 4,4 ', 4 "-triphenylmethane triisocyanates or lysine diisocyanate.
The chain extender is alcohol compound, aminated compounds or alcamine compound.Specially ethylene glycol, propylene glycol,
Diglycol, dipropylene glycol, 1,3-BDO, 1,4-butanediol, 1,5-PD, 3- methyl-1,5- pentanediol,
Butyl ethyl propylene glycol, diethyl pentanediol, ethohexadiol, neopentyl glycol, methyl propanediol, glycerine, trihydroxy methyl third
Alkane, trimethylolethane, 1,2,6- hexanetriol, pentaerythrite, Isosorbide-5-Nitrae-cyclohexanediol, hydrogenated bisphenol A, hydroquinone dihydroxy ethyl
Ether, ethanol amine, triisopropanolamine, methyl diethanolamine, 3,3 '-two chloro- 4,4 '-diphenyl methanes, 3,5- dimethyl sulphur-based toluene
Diamines, 4,4'- diaminodiphenylmethane, diethyl toluene diamine or triethanolamine.
The cyclic carbonate has：Ethylene carbonate, fluorinated ethylene carbonate, carbonic acid Asia vinylene, propene carbonate,
Chlorocarbonic acid acrylic ester, butylene, cyclohexene carbonate, vinyl cyclohexene carbonate, Styrene carbonate are double
Phenol A type cyclic carbonate, two cyclic carbonate of 1,4-butanediol, 1,2- cyclohexanediol, two cyclic carbonate, 3,4- cyclic carbonates
Ester hexahydrobenzoid acid -3 ', 4 '-cyclic carbonate ester methyl esters, 4,4 '-diaminodiphenyl ether, four cyclic carbonate, N, N, N ' N '-Fourth Ring
Four cyclic carbonate of shape carbonic ester -4,4 '-diaminodiphenylmethane or pentaerythrite.
The polymer polyatomic alcohol is that specially polyether polyol, polyester polyol, polyester ether polylol, polyolefin are polynary
One of alcohol, polycarbonate polyol, polycarbonate-polyether polyol are a variety of.
The tertiary amine catalyst can be triethylamine, N, N- dimethyl hexadecyl amine, diethylenetriamines, dimethyl
Benzylamine, N, N, N ' N '-tetramethyl methylene diamine, N, N, N, ' N '-tetramethylethylened, N, N, N ' N '-tetraethyl methylene
Base diamines, N, N, N ' N '-tetramethyl trimethylene diamine, N, N, N ' N '-tetramethylbutylene diamine, triethylenediamine, N- first
Base morpholine, N- dionin quinoline, N, N '-dimethyl piperazine, ethanol amine, diethanol amine, triethanolamine, dimethylethanolamine,
One of 1,8- diazabicylo-bicyclic (5,4,0) -7- hendecene, pyridine, lutidines etc. are a variety of.
Substantive distinguishing features of the invention are：
The method of the present invention introduces cyclic annular carbon during isocyanates reacts with polymer polyatomic alcohol and prepares polyurethane
Polyurethane-polyesteramide compound is prepared in situ in acid esters.By this method, directly the same of polyesteramide and polyurethane is being prepared
When form polyurethane-polyesteramide compound, can to avoid first buy or make by oneself obtain that polyurethane-could be prepared after polyurethane it is poly-
This tedious steps of amide compound.Material therefor is compared to referring to that method is more economical in current techniques, and this method institute
It can play that catalysis cyclic carbonate reacts with isocyanates generation polyesteramide and catalytic polymer is polynary simultaneously with catalyst
Alcohol reacts the effect for generating polyurethane with isocyanates.Existing chemical bonding between polyesteramide and polyurethane in gained compound
There is physical bond again.
Beneficial effects of the present invention are：It is introduced during polymer polyatomic alcohol reacts with isocyanates and prepares polyurethane
Cyclic carbonate is reacted with isocyanates, has been prepared in situ out a kind of polyurethane-polyesteramide compound.The compound is comprehensive
The advantages that having closed the higher modulus of polyesteramide and intensity, preferable wear-resisting and heat resistance and polyurethane are good elastic, resistance to
The advantages that oiliness, water resistance, high resiliency, can be widely applied to building, automobile manufacture, rag trade, household, electronics industry, medical treatment
Equal fields.
Detailed description of the invention
Fig. 1 is polycarbonate-polyether polyol (curve 1) in embodiment 1, polycarbonate-polyether polyol, propylene carbonate
Mixture (curve 2) and gained polyurethane-polyesteramide compound (curve 3) before ester and toluene di-isocyanate(TDI) reaction
The stacking chart of infrared spectroscopy.
Specific embodiment：
Below in conjunction with section Example, the present invention will be described, but is not intended to limit the present invention.
Experimental method described in the following example, no specified otherwise are conventional method.
The reagent and material are well known materials, and those skilled in the art can be made or obtain from commercial channels.
Polycarbonate-polyether polyol used in embodiment is provided by Jiangsu Zhongke Jinlong Chemical Co., Ltd., the equal molecule of number
Amount is 2700g/mol, and carbonate unit content is 42% (mole), and hydroxyl value is 42mg KOH/g.
Polyether polyol used in embodiment is provided by E.I.Du Pont Company, number-average molecular weight 2900g/mol, hydroxyl value 40mg
KOH/g。
Polyester polyol used in embodiment is provided by Beyer Co., Ltd, number-average molecular weight 2800g/mol, hydroxyl value 40mg
KOH/g。
Embodiment 1
Polycarbonate-polyether polyol is spare after vaccum dewatering 3 hours under the conditions of 110 DEG C；
Polycarbonate-polyether polyol 42.5g, propene carbonate 7.5g and trimethylolpropane 0.18g after removing water
(absolute pressure 0.01MPa, other steps and embodiment herewith vacuum degree) processing 1h is vacuumized in 60 DEG C.Wherein poly- carbonic acid
Ester-polyether polyol and the molar ratio of trimethylolpropane are 8.0；
After stopping vacuumizes, restore normal pressure, toluene di-isocyanate(TDI) 5.5g and triethylamine 50mg is added, after mixing evenly,
It injects in the mold of 60 DEG C of preheatings, reacts 1h, vacuumize process is carried out in reaction process to remove bubble.Wherein isocyanates rubs
The ratio of the total mole number of that number and the pure and mild propene carbonate of polycarbonate-polyether polyols is 0.6, and triethylamine dosage is poly- carbonic acid
The 0.1% of the pure and mild cyclic carbonate gross mass of ester-polyether polyols.
Stopping vacuumizes, and restores normal pressure, in 70 DEG C of reaction 2h, then 90 DEG C of solidification 12h.After demoulding, polyurethane-polyamides is obtained
Amine ester complexes.
This example has obtained the compound such as structural formula in technical solution, wherein R1、R2、R3It is followed successively by：
Product structure can be analyzed by infrared spectroscopy, polycarbonate-polyether polyol, polycarbonate-polyether polyols
Mixture and gained polyurethane-polyesteramide compound Fu before alcohol, propene carbonate and toluene di-isocyanate(TDI) reaction
In leaf infrared spectroscopy stacking chart it is as shown in Fig. 1.In Fig. 1, curve 1-3 is respectively polycarbonate-polyether polyol, poly- carbonic acid
Mixture and gained polyurethane-polyesteramide before ester-polyether polyol, propene carbonate and toluene di-isocyanate(TDI) reaction
The FTIR spectrum figure of compound.1748cm in curve 1-1And 1260cm-1The peak at place is respectively carbon oxygen on carbonic ester segment
The vibration absorption peak of double bond and carbon oxygen singly-bound, 1084cm-1Place is the absorption of carbon oxygen singly-bound on polyether segment, 3500cm-1Place is end
The absorption peak of hydroxyl；1809cm in curve 2-1Place is the vibration absorption peak of C=O bond on propene carbonate, 2272cm-1Place is
The characteristic absorption peak of isocyano；3350cm in curve 3-1Place is the absorption peak of-N-H-.The spy of isocyano and propene carbonate
Levy the disappearance of absorption peak, the appearance of-N-H- absorption peak, it was demonstrated that obtained polyurethane-polyesteramide compound.It can from infrared figure
To find out, the peak of isocyanates and cyclic carbonate disappears, this is because isocyanates not only with polyol reaction but also with cyclic annular carbon
Acid esters reaction, generates polyurethane and polyesteramide.Isocyanates can connect the two, and chain extender can also connect the two, formationization
It learns and combines.It can be seen that the absorption peak of-N-H- is wider from infrared figure, this is that-N-H- is formed with the carbonyl moiety on polyesteramide
Caused by hydrogen bond leads to red shift, it was demonstrated that there are physical bonds between polyurethane and polyamide.
Referring to national standard GB/T 528-1998《The measurement of vulcanized rubber or thermoplastic elastomer tensile stress-strain performance》It is right
Prepared polyurethane-polyesteramide compound carries out tensile strength and elongation at break test, as the result is shown its tensile strength
For 5.6MPa, elongation at break 413%.
Embodiment 2
Polyether polyol is spare after vaccum dewatering 3 hours under the conditions of 110 DEG C；
Polyether polyol 42.5g, propene carbonate 7.5g and trimethylolpropane 0.17g after removing water take out true in 60 DEG C
Manage 1h in vacancy.Wherein polycarbonate-polyether polyol and the molar ratio of trimethylolpropane are 8.0；
After stopping vacuumizes, restore normal pressure, toluene di-isocyanate(TDI) 5.4g and triethylamine 50mg is added, after mixing evenly,
It injects in the mold of 60 DEG C of preheatings, reacts 1h, vacuumize process is carried out in reaction process to remove bubble.Wherein isocyanates rubs
The ratio of the total mole number of that number and the pure and mild propene carbonate of polycarbonate-polyether polyols is 0.6, and triethylamine dosage is poly- carbonic acid
The 0.1% of the pure and mild cyclic carbonate gross mass of ester-polyether polyols.
Stopping vacuumizes, and restores normal pressure, in 70 DEG C of reaction 2h, then 90 DEG C of solidification 12h.After demoulding, compound is obtained.
Infrared spectrum characterization proves to have obtained polyurethane-polyesteramide compound.In the composite structure that this example obtains,
R1、R2、R3It is followed successively by：
Embodiment 3
Polyester polyol is spare after vaccum dewatering 3 hours under the conditions of 110 DEG C；
Polyether polyol 42.5g, propene carbonate 7.5g and trimethylolpropane 0.17g after removing water take out true in 60 DEG C
Manage 1h in vacancy.Wherein polycarbonate-polyether polyol and the molar ratio of trimethylolpropane are 8.0；
After stopping vacuumizes, restore normal pressure, toluene di-isocyanate(TDI) 5.4g and triethylamine 50mg is added, after mixing evenly,
It injects in the mold of 60 DEG C of preheatings, reacts 1h, vacuumize process is carried out in reaction process to remove bubble.Wherein isocyanates rubs
The ratio of the total mole number of that number and the pure and mild propene carbonate of polycarbonate-polyether polyols is 0.6, and triethylamine dosage is poly- carbonic acid
The 0.1% of the pure and mild cyclic carbonate gross mass of ester-polyether polyols.
Stopping vacuumizes, and restores normal pressure, in 70 DEG C of reaction 2h, then 90 DEG C of solidification 12h.After demoulding, compound is obtained.
Infrared spectrum characterization proves to have obtained polyurethane-polyesteramide compound.In the composite structure that this example obtains,
R1、R2、R3It is followed successively by：
Embodiment 4
Polycarbonate-polyether polyol is spare after vaccum dewatering 3 hours under the conditions of 110 DEG C；
Polycarbonate-polyether polyol 42.5g, propene carbonate 7.5g and trimethylolpropane 0.18g after removing water
In 60 DEG C of vacuumize process 1h.Wherein polycarbonate-polyether polyol and the molar ratio of trimethylolpropane are 8.0；
After stopping vacuumizes, restore normal pressure, toluene di-isocyanate(TDI) 7.3g and triethylamine 50mg is added, after mixing evenly,
It injects in the mold of 60 DEG C of preheatings, reacts 1h, vacuumize process is carried out in reaction process to remove bubble.Wherein isocyanates rubs
The ratio of the total mole number of that number and the pure and mild propene carbonate of polycarbonate-polyether polyols is 0.8, and triethylamine dosage is poly- carbonic acid
The 0.1% of the pure and mild cyclic carbonate gross mass of ester-polyether polyols.
Stopping vacuumizes, and restores normal pressure, in 70 DEG C of reaction 2h, then 90 DEG C of solidification 12h.After demoulding, compound is obtained.
Infrared spectrum characterization proves to have obtained polyurethane-polyesteramide compound.In the composite structure that this example obtains,
R1、R2、R3It is followed successively by：
Embodiment 5
Polycarbonate-polyether polyol is spare after vaccum dewatering 3 hours under the conditions of 110 DEG C；
Polycarbonate-polyether polyol 42.5g, propene carbonate 7.5g and trimethylolpropane 0.18g after removing water
In 60 DEG C of vacuumize process 1h.Wherein polycarbonate-polyether polyol and the molar ratio of trimethylolpropane are 8.0；
After stopping vacuumizes, restore normal pressure, toluene di-isocyanate(TDI) 9.2g and triethylamine 50mg is added, after mixing evenly,
It injects in the mold of 60 DEG C of preheatings, reacts 1h, vacuumize process is carried out in reaction process to remove bubble.Wherein isocyanates rubs
The ratio of the total mole number of that number and the pure and mild propene carbonate of polycarbonate-polyether polyols is 1.0, and triethylamine dosage is poly- carbonic acid
The 0.1% of the pure and mild cyclic carbonate gross mass of ester-polyether polyols.
Stopping vacuumizes, and restores normal pressure, in 70 DEG C of reaction 2h, then 90 DEG C of solidification 12h.After demoulding, ester complexes are obtained.
Infrared spectrum characterization proves to have obtained polyurethane-polyesteramide compound.In the composite structure that this example obtains,
R1、R2、R3It is followed successively by：
Embodiment 6
Polycarbonate-polyether polyol is spare after vaccum dewatering 3 hours under the conditions of 110 DEG C；
Polycarbonate-polyether polyol 42.5g, propene carbonate 7.5g and trimethylolpropane 0.18g after removing water
In 60 DEG C of vacuumize process 1h.Wherein polycarbonate-polyether polyol and the molar ratio of trimethylolpropane are 8.0；
After stopping vacuumizes, restore normal pressure, toluene di-isocyanate(TDI) 10.1g and triethylamine 50mg is added, after mixing evenly,
It injects in the mold of 60 DEG C of preheatings, reacts 1h, vacuumize process is carried out in reaction process to remove bubble.Wherein isocyanates rubs
The ratio of the total mole number of that number and the pure and mild propene carbonate of polycarbonate-polyether polyols is 1.1, and triethylamine dosage is poly- carbonic acid
The 0.1% of the pure and mild cyclic carbonate gross mass of ester-polyether polyols.
Stopping vacuumizes, and restores normal pressure, in 70 DEG C of reaction 2h, then 90 DEG C of solidification 12h.After demoulding, compound is obtained.
Infrared spectrum characterization proves to have obtained polyurethane-polyesteramide compound.In the composite structure that this example obtains,
R1、R2、R3It is followed successively by：
Embodiment 7
Polycarbonate-polyether polyol is spare after vaccum dewatering 3 hours under the conditions of 110 DEG C；
Polycarbonate-polyether polyol 42.5g, propene carbonate 7.5g and trimethylolpropane 0.18g after removing water
In 60 DEG C of vacuumize process 1h.Wherein polycarbonate-polyether polyol and the molar ratio of trimethylolpropane are 8.0；
After stopping vacuumizes, restore normal pressure, toluene di-isocyanate(TDI) 12.8g and triethylamine 50mg is added, after mixing evenly,
It injects in the mold of 60 DEG C of preheatings, reacts 1h, vacuumize process is carried out in reaction process to remove bubble.Wherein isocyanates rubs
The ratio of the total mole number of that number and the pure and mild propene carbonate of polycarbonate-polyether polyols is 1.4, and triethylamine dosage is poly- carbonic acid
The 0.1% of the pure and mild cyclic carbonate gross mass of ester-polyether polyols.
Stopping vacuumizes, and restores normal pressure, in 70 DEG C of reaction 2h, then 90 DEG C of solidification 12h.After demoulding, compound is obtained.
Infrared spectrum characterization proves to have obtained polyurethane-polyesteramide compound.In the composite structure that this example obtains,
R1、R2、R3It is followed successively by：
Embodiment 8
Polycarbonate-polyether polyol is spare after vaccum dewatering 3 hours under the conditions of 110 DEG C；
Polycarbonate-polyether polyol 45g, propene carbonate 5g and trimethylolpropane 0.19g after removing water is in 60
DEG C vacuumize process 1h.Wherein polycarbonate-polyether polyol and the molar ratio of trimethylolpropane are 8.0；
After stopping vacuumizes, restore normal pressure, toluene di-isocyanate(TDI) 5.8g and triethylamine 50mg is added, after mixing evenly,
It injects in the mold of 60 DEG C of preheatings, reacts 1h, vacuumize process is carried out in reaction process to remove bubble.Wherein isocyanates rubs
The ratio of the total mole number of that number and the pure and mild propene carbonate of polycarbonate-polyether polyols is 0.8, and triethylamine dosage is poly- carbonic acid
The 0.1% of the pure and mild cyclic carbonate gross mass of ester-polyether polyols.
Stopping vacuumizes, and restores normal pressure, in 70 DEG C of reaction 2h, then 90 DEG C of solidification 12h.After demoulding, compound is obtained.
Infrared spectrum characterization proves to have obtained polyurethane-polyesteramide compound.In the composite structure that this example obtains,
R1、R2、R3It is followed successively by：
Embodiment 9
Polycarbonate-polyether polyol is spare after vaccum dewatering 3 hours under the conditions of 110 DEG C；
Polycarbonate-polyether polyol 40g, propene carbonate 10g and trimethylolpropane 0.17g after removing water is in 60
DEG C vacuumize process 1h.Wherein polycarbonate-polyether polyol and the molar ratio of trimethylolpropane are 8.0；
After stopping vacuumizes, restore normal pressure, toluene di-isocyanate(TDI) 8.9g and triethylamine 50mg is added, after mixing evenly,
It injects in the mold of 60 DEG C of preheatings, reacts 1h, vacuumize process is carried out in reaction process to remove bubble.Wherein isocyanates rubs
The ratio of the total mole number of that number and the pure and mild propene carbonate of polycarbonate-polyether polyols is 0.8, and triethylamine dosage is poly- carbonic acid
The 0.1% of the pure and mild cyclic carbonate gross mass of ester-polyether polyols.
Stopping vacuumizes, and restores normal pressure, in 70 DEG C of reaction 2h, then 90 DEG C of solidification 12h.After demoulding, compound is obtained.
Infrared spectrum characterization proves to have obtained polyurethane-polyesteramide compound.In the composite structure that this example obtains,
R1、R2、R3It is followed successively by：
Embodiment 10
Polycarbonate-polyether polyol is spare after vaccum dewatering 3 hours under the conditions of 110 DEG C；
Polycarbonate-polyether polyol 35g, propene carbonate 15g and trimethylolpropane 0.15g after removing water is in 60
DEG C vacuumize process 1h.Wherein polycarbonate-polyether polyol and the molar ratio of trimethylolpropane are 8.0；
After stopping vacuumizes, restore normal pressure, toluene di-isocyanate(TDI) 12.0g and triethylamine 50mg is added, after mixing evenly,
It injects in the mold of 60 DEG C of preheatings, reacts 1h, vacuumize process is carried out in reaction process to remove bubble.Wherein isocyanates rubs
The ratio of the total mole number of that number and the pure and mild propene carbonate of polycarbonate-polyether polyols is 0.8, and triethylamine dosage is poly- carbonic acid
The 0.1% of the pure and mild cyclic carbonate gross mass of ester-polyether polyols.
Stopping vacuumizes, and restores normal pressure, in 70 DEG C of reaction 2h, then 90 DEG C of solidification 12h.After demoulding, compound is obtained.
Infrared spectrum characterization proves to have obtained polyurethane-polyesteramide compound.In the composite structure that this example obtains,
R1、R2、R3It is followed successively by：
Embodiment 11
Polycarbonate-polyether polyol is spare after vaccum dewatering 3 hours under the conditions of 110 DEG C；
Polycarbonate-polyether polyol 30g, propene carbonate 20g and trimethylolpropane 0.13g after removing water is in 60
DEG C vacuumize process 1h.Wherein polycarbonate-polyether polyol and the molar ratio of trimethylolpropane are 8.0；
After stopping vacuumizes, restore normal pressure, toluene di-isocyanate(TDI) 15.2g and triethylamine 50mg is added, after mixing evenly,
It injects in the mold of 60 DEG C of preheatings, reacts 1h, vacuumize process is carried out in reaction process to remove bubble.Wherein isocyanates rubs
The ratio of the total mole number of that number and the pure and mild propene carbonate of polycarbonate-polyether polyols is 0.8, and triethylamine dosage is poly- carbonic acid
The 0.1% of the pure and mild cyclic carbonate gross mass of ester-polyether polyols.
Stopping vacuumizes, and restores normal pressure, in 70 DEG C of reaction 2h, then 90 DEG C of solidification 12h.After demoulding, compound is obtained.
Infrared spectrum characterization proves to have obtained polyurethane-polyesteramide compound.In the composite structure that this example obtains,
R1、R2、R3It is followed successively by：
Embodiment 12
Polycarbonate-polyether polyol is spare after vaccum dewatering 3 hours under the conditions of 110 DEG C；
Polycarbonate-polyether polyol 47g, propene carbonate 3g and trimethylolpropane 0.20g after removing water is in 60
DEG C vacuumize process 1h.Wherein polycarbonate-polyether polyol and the molar ratio of trimethylolpropane are 8.0；
After stopping vacuumizes, restore normal pressure, toluene di-isocyanate(TDI) 4.5g and triethylamine 50mg is added, after mixing evenly,
It injects in the mold of 60 DEG C of preheatings, reacts 1h, vacuumize process is carried out in reaction process to remove bubble.Wherein isocyanates rubs
The ratio of the total mole number of that number and the pure and mild propene carbonate of polycarbonate-polyether polyols is 0.8, and triethylamine dosage is poly- carbonic acid
The 0.1% of the pure and mild cyclic carbonate gross mass of ester-polyether polyols.
Stopping vacuumizes, and restores normal pressure, in 70 DEG C of reaction 2h, then 90 DEG C of solidification 12h.After demoulding, compound is obtained.
Infrared spectrum characterization proves to have obtained polyurethane-polyesteramide compound.In the composite structure that this example obtains,
R1、R2、R3It is followed successively by：
Embodiment 13
Polycarbonate-polyether polyol is spare after vaccum dewatering 3 hours under the conditions of 110 DEG C；
Polycarbonate-polyether polyol 49g, propene carbonate 1g and trimethylolpropane 0.21g after removing water is in 60
DEG C vacuumize process 1h.Wherein polycarbonate-polyether polyol and the molar ratio of trimethylolpropane are 8.0；
After stopping vacuumizes, restore normal pressure, toluene di-isocyanate(TDI) 3.2g and triethylamine 50mg is added, after mixing evenly,
It injects in the mold of 60 DEG C of preheatings, reacts 1h, vacuumize process is carried out in reaction process to remove bubble.Wherein isocyanates rubs
The ratio of the total mole number of that number and the pure and mild propene carbonate of polycarbonate-polyether polyols is 0.8, and triethylamine dosage is poly- carbonic acid
The 0.1% of the pure and mild cyclic carbonate gross mass of ester-polyether polyols.
Stopping vacuumizes, and restores normal pressure, in 70 DEG C of reaction 2h, then 90 DEG C of solidification 12h.After demoulding, compound is obtained.
Infrared spectrum characterization proves to have obtained polyurethane-polyesteramide compound.In the composite structure that this example obtains,
R1、R2、R3It is followed successively by：
Embodiment 14
Polycarbonate-polyether polyol is spare after vaccum dewatering 3 hours under the conditions of 110 DEG C；
Polycarbonate-polyether polyol 40g, propene carbonate 10g and trimethylolpropane 0.19g after removing water is in 60
DEG C vacuumize process 1h.Wherein polycarbonate-polyether polyol and the molar ratio of trimethylolpropane are 8.0；
After stopping vacuumizes, restore normal pressure, toluene di-isocyanate(TDI) 5.8g and ethanol amine 50mg is added, after mixing evenly,
It injects in the mold of 60 DEG C of preheatings, reacts 1h, vacuumize process is carried out in reaction process to remove bubble.Wherein isocyanates rubs
The ratio of the total mole number of that number and the pure and mild propene carbonate of polycarbonate-polyether polyols is 0.8, and ethanol amine dosage is poly- carbonic acid
The 0.1% of the pure and mild cyclic carbonate gross mass of ester-polyether polyols.
Stopping vacuumizes, and restores normal pressure, in 70 DEG C of reaction 2h, then 90 DEG C of solidification 12h.After demoulding, compound is obtained.
Infrared spectrum characterization proves to have obtained polyurethane-polyesteramide compound.In the composite structure that this example obtains,
R1、R2、R3It is followed successively by：
Embodiment 15
Polycarbonate-polyether polyol is spare after vaccum dewatering 3 hours under the conditions of 110 DEG C；
Polycarbonate-polyether polyol 40g, propene carbonate 10g and trimethylolpropane 0.19g after removing water is in 60
DEG C vacuumize process 1h.Wherein polycarbonate-polyether polyol and the molar ratio of trimethylolpropane are 8.0；
After stopping vacuumizes, restore normal pressure, toluene di-isocyanate(TDI) 5.8g and diethanol amine 50mg is added, stirs evenly
Afterwards, it injects in the mold of 60 DEG C of preheatings, reacts 1h, vacuumize process is carried out in reaction process to remove bubble.Wherein isocyanic acid
The ratio of the total mole number of ester molal quantity and the pure and mild propene carbonate of polycarbonate-polyether polyols is 0.8, and diethanol amine dosage is poly-
The 0.1% of the pure and mild cyclic carbonate gross mass of carbonic ester-polyether polyols.
Stopping vacuumizes, and restores normal pressure, in 70 DEG C of reaction 2h, then 90 DEG C of solidification 12h.After demoulding, compound is obtained.
Infrared spectrum characterization proves to have obtained polyurethane-polyesteramide compound.In the composite structure that this example obtains,
R1、R2、R3It is followed successively by：
Embodiment 16
Polycarbonate-polyether polyol is spare after vaccum dewatering 3 hours under the conditions of 110 DEG C；
Polycarbonate-polyether polyol 40g, propene carbonate 10g and trimethylolpropane 0.19g after removing water is in 60
DEG C vacuumize process 1h.Wherein polycarbonate-polyether polyol and the molar ratio of trimethylolpropane are 8.0；
After stopping vacuumizes, restore normal pressure, toluene di-isocyanate(TDI) 5.8g and triethanolamine 50mg is added, stirs evenly
Afterwards, it injects in the mold of 60 DEG C of preheatings, reacts 1h, vacuumize process is carried out in reaction process to remove bubble.Wherein isocyanic acid
The ratio of the total mole number of ester molal quantity and the pure and mild propene carbonate of polycarbonate-polyether polyols is 0.8, and triethanolamine dosage is poly-
The 0.1% of the pure and mild cyclic carbonate gross mass of carbonic ester-polyether polyols.
Stopping vacuumizes, and restores normal pressure, in 70 DEG C of reaction 2h, then 90 DEG C of solidification 12h.After demoulding, compound is obtained.
Infrared spectrum characterization proves to have obtained polyurethane-polyesteramide compound.In the composite structure that this example obtains,
R1、R2、R3It is followed successively by：
Embodiment 17
Polycarbonate-polyether polyol is spare after vaccum dewatering 3 hours under the conditions of 110 DEG C；
Polycarbonate-polyether polyol 42.5g, propene carbonate 7.5g and 1,4- butanediol 0.18g after removing water in
60 DEG C of vacuumize process 1h.Wherein polycarbonate-polyether polyol and the molar ratio of 1,4- butanediol are 8.0；
After stopping vacuumizes, restore normal pressure, toluene di-isocyanate(TDI) 5.5g and triethylamine 50mg is added, after mixing evenly,
It injects in the mold of 60 DEG C of preheatings, reacts 1h, vacuumize process is carried out in reaction process to remove bubble.Wherein isocyanates rubs
The ratio of the total mole number of that number and the pure and mild propene carbonate of polycarbonate-polyether polyols is 0.8, and triethylamine dosage is poly- carbonic acid
The 0.1% of the pure and mild cyclic carbonate gross mass of ester-polyether polyols.
Stopping vacuumizes, and restores normal pressure, in 70 DEG C of reaction 2h, then 90 DEG C of solidification 12h.After demoulding, compound is obtained.
Infrared spectrum characterization proves to have obtained polyurethane-polyesteramide compound.In the composite structure that this example obtains,
R1、R2、R3It is followed successively by：
Embodiment 18
Polycarbonate-polyether polyol is spare after vaccum dewatering 3 hours under the conditions of 110 DEG C；
Polycarbonate-polyether polyol 42.5g, propene carbonate 7.5g and pentaerythrite 0.14g after removing water is in 60
DEG C vacuumize process 1h.Wherein polycarbonate-polyether polyol and the molar ratio of pentaerythrite are 8.0；
After stopping vacuumizes, restore normal pressure, toluene di-isocyanate(TDI) 5.5g and triethylamine 50mg is added, after mixing evenly,
It injects in the mold of 60 DEG C of preheatings, reacts 1h, vacuumize process is carried out in reaction process to remove bubble.Wherein isocyanates rubs
The ratio of the total mole number of that number and the pure and mild propene carbonate of polycarbonate-polyether polyols is 0.8, and triethylamine dosage is poly- carbonic acid
The 0.1% of the pure and mild cyclic carbonate gross mass of ester-polyether polyols.
Stopping vacuumizes, and restores normal pressure, in 70 DEG C of reaction 2h, then 90 DEG C of solidification 12h.After demoulding, compound is obtained.
Infrared spectrum characterization proves to have obtained polyurethane-polyesteramide compound.In the composite structure that this example obtains,
R1、R2、R3It is followed successively by：
Embodiment 19
Polycarbonate-polyether polyol is spare after vaccum dewatering 3 hours under the conditions of 110 DEG C；
Polycarbonate-polyether polyol 42.5g, propene carbonate 7.5g and glycerine 0.12g after removing water is in 60 DEG C
Vacuumize process 1h.Wherein polycarbonate-polyether polyol and the molar ratio of glycerine are 8.0；
After stopping vacuumizes, restore normal pressure, toluene di-isocyanate(TDI) 5.5g and triethylamine 50mg is added, after mixing evenly,
It injects in the mold of 60 DEG C of preheatings, reacts 1h, vacuumize process is carried out in reaction process to remove bubble.Wherein isocyanates rubs
The ratio of the total mole number of that number and the pure and mild propene carbonate of polycarbonate-polyether polyols is 0.8, and triethylamine dosage is poly- carbonic acid
The 0.1% of the pure and mild cyclic carbonate gross mass of ester-polyether polyols.
Stopping vacuumizes, and restores normal pressure, in 70 DEG C of reaction 2h, then 90 DEG C of solidification 12h.After demoulding, compound is obtained.
Infrared spectrum characterization proves to have obtained polyurethane-polyesteramide compound.In the composite structure that this example obtains,
R1、R2、R3It is followed successively by：
Embodiment 20
Polycarbonate-polyether polyol is spare after vaccum dewatering 3 hours under the conditions of 110 DEG C；
Polycarbonate-polyether polyol 42.5g, propene carbonate 7.5g and trimethylolpropane 0.18g after removing water
In 60 DEG C of vacuumize process 1h.Wherein polycarbonate-polyether polyol and the molar ratio of trimethylolpropane are 8.0；
After stopping vacuumizes, restore normal pressure, hexamethylene diisocyanate 5.3g and triethylamine 50mg is added, stirs evenly
Afterwards, it injects in the mold of 60 DEG C of preheatings, reacts 1h, vacuumize process is carried out in reaction process to remove bubble.Wherein isocyanic acid
The ratio of the total mole number of ester molal quantity and the pure and mild propene carbonate of polycarbonate-polyether polyols is 0.8, and triethylamine dosage is poly- carbon
The 0.1% of the pure and mild cyclic carbonate gross mass of acid esters-polyether polyols.
Stopping vacuumizes, and restores normal pressure, in 70 DEG C of reaction 2h, then 90 DEG C of solidification 12h.After demoulding, compound is obtained.
Infrared spectrum characterization proves to have obtained polyurethane-polyesteramide compound.In the composite structure that this example obtains,
R1、R2、R3It is followed successively by：
Embodiment 21
Polycarbonate-polyether polyol is spare after vaccum dewatering 3 hours under the conditions of 110 DEG C；
Polyether polyol 42.5g, propene carbonate 7.5g and trimethylolpropane 0.17g after removing water take out true in 60 DEG C
Manage 1h in vacancy.Wherein polycarbonate-polyether polyol and the molar ratio of trimethylolpropane are 8.0；
After stopping vacuumizes, restore normal pressure, methyl diphenylene diisocyanate 7.8g and triethylamine 50mg is added, stirring is equal
It after even, injects in the mold of 60 DEG C of preheatings, reacts 1h, vacuumize process is carried out in reaction process to remove bubble.Wherein isocyanide
The ratio of the total mole number of acid esters molal quantity and the pure and mild propene carbonate of polyether polyols is 0.8, and triethylamine dosage is poly- for polycarbonate-
The 0.1% of ethoxylated polyhydric alcohol and cyclic carbonate gross mass.
Stopping vacuumizes, and restores normal pressure, in 70 DEG C of reaction 2h, then 90 DEG C of solidification 12h.After demoulding, compound is obtained.
Infrared spectrum characterization proves to have obtained polyurethane-polyesteramide compound.In the composite structure that this example obtains,
R1、R2、R3It is followed successively by：
Embodiment 22
Polycarbonate-polyether polyol is spare after vaccum dewatering 3 hours under the conditions of 110 DEG C；
Polyester polyol 42.5g, propene carbonate 7.5g and trimethylolpropane 0.17g after removing water take out true in 60 DEG C
Manage 1h in vacancy.Wherein polycarbonate-polyether polyol and the molar ratio of trimethylolpropane are 8.0；
After stopping vacuumizes, restore normal pressure, isophorone diisocyanate 6.9g and triethylamine 50mg is added, stirs evenly
Afterwards, it injects in the mold of 60 DEG C of preheatings, reacts 1h, vacuumize process is carried out in reaction process to remove bubble.Wherein isocyanic acid
The ratio of the total mole number of ester molal quantity and the pure and mild propene carbonate of polyester polyols is 0.8, and triethylamine dosage is that polyester polyols are pure and mild
The 0.1% of cyclic carbonate gross mass.
Stopping vacuumizes, and restores normal pressure, in 70 DEG C of reaction 2h, then 90 DEG C of solidification 12h.After demoulding, compound is obtained.
Infrared spectrum characterization proves to have obtained polyurethane-polyesteramide compound.In the composite structure that this example obtains,
R1、R2、R3It is followed successively by：
Embodiment 23
Polycarbonate-polyether polyol is spare after vaccum dewatering 3 hours under the conditions of 110 DEG C；
Polycarbonate-polyether polyol 42.5g, ethylene carbonate 6.5g and trimethylolpropane 0.18g after removing water
In 60 DEG C of vacuumize process 1h.Wherein polycarbonate-polyether polyol and the molar ratio of trimethylolpropane are 8.0；
After stopping vacuumizes, restore normal pressure, toluene di-isocyanate(TDI) 5.5g and triethylamine 49mg is added, after mixing evenly,
It injects in the mold of 60 DEG C of preheatings, reacts 1h, vacuumize process is carried out in reaction process to remove bubble.Wherein isocyanates rubs
The ratio of the total mole number of that number and the pure and mild ethylene carbonate of polycarbonate-polyether polyols is 0.6, and triethylamine dosage is poly- carbonic acid
The 0.1% of the pure and mild cyclic carbonate gross mass of ester-polyether polyols.
Stopping vacuumizes, and restores normal pressure, in 70 DEG C of reaction 2h, then 90 DEG C of solidification 12h.After demoulding, compound is obtained.
Infrared spectrum characterization proves to have obtained polyurethane-polyesteramide compound.In the composite structure that this example obtains,
R1、R2、R3It is followed successively by：
Embodiment 24
Polycarbonate-polyether polyol is spare after vaccum dewatering 3 hours under the conditions of 110 DEG C；
Polycarbonate-polyether polyol 42.5g, fluorinated ethylene carbonate 7.8g and trimethylolpropane after removing water
0.18g is in 60 DEG C of vacuumize process 1h.Wherein polycarbonate-polyether polyol and the molar ratio of trimethylolpropane are 8.0；
After stopping vacuumizes, restore normal pressure, toluene di-isocyanate(TDI) 5.5g and triethylamine 50mg is added, after mixing evenly,
It injects in the mold of 60 DEG C of preheatings, reacts 1h, vacuumize process is carried out in reaction process to remove bubble.Wherein isocyanates rubs
The ratio of the total mole number of that number and the pure and mild fluorinated ethylene carbonate of polycarbonate-polyether polyols is 0.6, and triethylamine dosage is poly- carbon
The 0.1% of the pure and mild cyclic carbonate gross mass of acid esters-polyether polyols.
Stopping vacuumizes, and restores normal pressure, in 70 DEG C of reaction 2h, then 90 DEG C of solidification 12h.After demoulding, compound is obtained.
Infrared spectrum characterization proves to have obtained polyurethane-polyesteramide compound.In the composite structure that this example obtains,
R1、R2、R3It is followed successively by：
Embodiment 25
Polycarbonate-polyether polyol is spare after vaccum dewatering 3 hours under the conditions of 110 DEG C；
Polycarbonate-polyether polyol 42.5g, chlorocarbonic acid acrylic ester 10.0g and trimethylolpropane after removing water
0.18g is in 60 DEG C of vacuumize process 1h.Wherein polycarbonate-polyether polyol and the molar ratio of trimethylolpropane are 8.0；
After stopping vacuumizes, restore normal pressure, toluene di-isocyanate(TDI) 5.5g and triethylamine 52mg is added, after mixing evenly,
It injects in the mold of 60 DEG C of preheatings, reacts 1h, vacuumize process is carried out in reaction process to remove bubble.Wherein isocyanates rubs
The ratio of the total mole number of that number and the pure and mild chlorocarbonic acid acrylic ester of polycarbonate-polyether polyols is 0.6, and triethylamine dosage is poly- carbon
The 0.1% of the pure and mild cyclic carbonate gross mass of acid esters-polyether polyols.
Stopping vacuumizes, and restores normal pressure, in 70 DEG C of reaction 2h, then 90 DEG C of solidification 12h.After demoulding, compound is obtained.
Infrared spectrum characterization proves to have obtained polyurethane-polyesteramide compound.In the composite structure that this example obtains,
R1、R2、R3It is followed successively by：
Above embodiments may indicate that the wider Reaction conditions range of the method for the present invention.
Above embodiments, which are only to aid in, understands method and core concept of the invention.In the condition for not departing from the principle of the invention
Under, it can be with several improvements and modifications are made to the present invention, these improvement and modification will also fall claim of the invention to the greatest extent
Within protection scope.Meanwhile the present invention will not be limited to above-described embodiment, and be to fit to the present invention shown in principle and
The consistent widest range of features of novelty.
Isocyanates described in this patent and its corresponding R1It can be one of following table, but be not limited to listed compound：
Chain extender described in this patent and its corresponding R2Specially one of following table, but it is not limited to listed compound：
The cyclic carbonate and its corresponding R3Specially one of following table, but it is not limited to listed compound：
Unaccomplished matter of the present invention is well-known technique.
Claims (6)
1. a kind of polyurethane-polyesteramide compound, it is characterized in that the chemical structural formula of the compound is as follows：
Wherein, R1、R2、R3It is alkyl or substituted hydrocarbon radical；
The polyurethane-polyesteramide compound preparation method, includes the following steps：
(1) polymer polyatomic alcohol is spare after vaccum dewatering 3h-6h under the conditions of 90 DEG C -120 DEG C；
(2) by polymer polyatomic alcohol, cyclic carbonate and chain extender by dehydration in 40 DEG C of -80 DEG C of vacuumize process 1h-3h；
Wherein, molar ratio is polymer polyatomic alcohol：Chain extender=2.0-16.0：1；Mass ratio is cyclic carbonate：Polymer polyatomic alcohol
=0.1-10：10；
(3) restore normal pressure, isocyanates and tertiary amine catalyst is added, after mixing evenly, the mold of 40 DEG C of -80 DEG C of preheatings of injection
In, 1h-3h is reacted, then vacuumizing and defoaming；Wherein, molar ratio is isocyanates：Polymer polyatomic alcohol and cyclic carbonate it
With=0.6-1.4：1；Tertiary amine catalyst is the 0.1%-5% of the pure and mild cyclic carbonate gross mass of polymer polyol；
(4) the reaction was continued at lower 40 DEG C -80 DEG C of normal pressure 2h-6h, then 90 DEG C of -120 DEG C of solidification 12h-24h；
(5) after demoulding, polyurethane-polyesteramide compound is obtained；
The isocyanates is aromatic isocyanate, aliphatic isocyanates or alicyclic isocyanate；
The chain extender is alcohol compound, aminated compounds or alcamine compound；
The cyclic carbonate is specially ethylene carbonate, fluorinated ethylene carbonate, vinylene carbonate, propene carbonate, chlorine
For propene carbonate, butylene, cyclohexene carbonate, vinyl cyclohexene carbonate, Styrene carbonate, bis-phenol
A type cyclic carbonate, two cyclic carbonate of 1,4-butanediol, 1,2- cyclohexanediol, two cyclic carbonate, 3,4- cyclic carbonates
Hexahydrobenzoid acid -3 ', 4 '-cyclic carbonate ester methyl esters, 4,4 '-diaminodiphenyl ether, four cyclic carbonate, N, N, N ', the Fourth Ring N ' -
Four cyclic carbonate of shape carbonic ester -4,4 '-diaminodiphenylmethane or pentaerythrite.
2. polyurethane as described in claim 1-polyesteramide compound preparation method, it is characterized in that including the following steps：
(1) polymer polyatomic alcohol is spare after vaccum dewatering 3h-6h under the conditions of 90 DEG C -120 DEG C；
(2) by polymer polyatomic alcohol, cyclic carbonate and chain extender by dehydration in 40 DEG C of -80 DEG C of vacuumize process 1h-3h；
Wherein, molar ratio is polymer polyatomic alcohol：Chain extender=2.0-16.0：1；Mass ratio is cyclic carbonate：Polymer polyatomic alcohol
=0.1-10：10；
(3) restore normal pressure, isocyanates and tertiary amine catalyst is added, after mixing evenly, the mold of 40 DEG C of -80 DEG C of preheatings of injection
In, 1h-3h is reacted, then vacuumizing and defoaming；Wherein, molar ratio is isocyanates：Polymer polyatomic alcohol and cyclic carbonate it
With=0.6-1.4：1；Tertiary amine catalyst is the 0.1%-5% of the pure and mild cyclic carbonate gross mass of polymer polyol；
(4) the reaction was continued at lower 40 DEG C -80 DEG C of normal pressure 2h-6h, then 90 DEG C of -120 DEG C of solidification 12h-24h；
(5) after demoulding, polyurethane-polyesteramide compound is obtained；
The isocyanates is aromatic isocyanate, aliphatic isocyanates or alicyclic isocyanate；
The chain extender is alcohol compound, aminated compounds or alcamine compound；
The cyclic carbonate is specially ethylene carbonate, fluorinated ethylene carbonate, vinylene carbonate, propene carbonate, chlorine
For propene carbonate, butylene, cyclohexene carbonate, vinyl cyclohexene carbonate, Styrene carbonate, bis-phenol
A type cyclic carbonate, two cyclic carbonate of 1,4-butanediol, 1,2- cyclohexanediol, two cyclic carbonate, 3,4- cyclic carbonates
Hexahydrobenzoid acid -3 ', 4 '-cyclic carbonate ester methyl esters, 4,4 '-diaminodiphenyl ether, four cyclic carbonate, N, N, N ', the Fourth Ring N ' -
Four cyclic carbonate of shape carbonic ester -4,4 '-diaminodiphenylmethane or pentaerythrite.
3. polyurethane as claimed in claim 2-polyesteramide compound preparation method, it is characterized in that the polymer polyol
Alcohol is specially polyether polyol, polyester polyol, polyester ether polylol, polyolefin polyhydric alcohol, polycarbonate polyol, poly- carbonic acid
One of ester-polyether polyol is a variety of.
4. polyurethane as claimed in claim 2-polyesteramide compound preparation method, it is characterized in that the tertiary amines are urged
Agent can be triethylamine, N, N- dimethyl (cetyl) amine, diethylenetriamines, dimethyl benzylamine, N, N, N ', N '-tetramethyl
Methylene diamines, N, N, N, ' N '-tetramethylethylened, N, N, N ', N '-tetraethyl methylene diamine, N, N, N ' and, N '-
Tetramethyl trimethylene diamine, N, N, N ', N '-tetramethylbutylene diamine, triethylenediamine, N- methylmorpholine, N- ethyl
Morpholine, N, N '-dimethyl piperazine, triethanolamine, dimethylethanolamine, 1,8- diazabicylo-bicyclic (5,4,0) -7- ten
One of one alkene, pyridine, lutidines etc. are a variety of.
5. polyurethane as claimed in claim 2-polyesteramide compound preparation method, it is characterized in that the isocyanates has
Body is toluene di-isocyanate(TDI), methyl diphenylene diisocyanate, paraphenylene diisocyanate, 3,3'- dimethyl -4,4'- biphenyl
Diisocyanate, 3,3 '-dichloro- biphenyl -4,4 '-diisocyanate, hexamethylene diisocyanate, 1,5- naphthalene diisocyanate
Ester, isophorone diisocyanate, 4,4 '-hexylmethanes, O-phthalic group diisocyanate, trimethyl
Hexamethylene diisocyanate, 4,4 ', 4 "-triphenylmethane triisocyanates or lysine diisocyanate.
6. polyurethane as claimed in claim 2-polyesteramide compound preparation method, it is characterized in that the chain extender is specific
For ethylene glycol, propylene glycol, diglycol, dipropylene glycol, 1,3-BDO, 1,4-butanediol, 1,5-PD, 3-
Methyl-1,5- pentanediol, butyl ethyl propylene glycol, diethyl pentanediol, ethohexadiol, neopentyl glycol, methyl propanediol, third
Triol, trimethylolpropane, trimethylolethane, 1,2,6- hexanetriol, pentaerythrite, Isosorbide-5-Nitrae-cyclohexanediol, hydrogenated bisphenol A,
Hydroquinone two hydroxy ethyl ether, ethanol amine, triisopropanolamine, methyl diethanolamine, 3,3 '-two chloro- 4,4 '-diphenyl methanes,
3,5- dimethythiotoluene diamines, 4,4'- diaminodiphenylmethane, diethyl toluene diamine or triethanolamine.
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| CN109456459B (en) * | 2018-09-30 | 2021-06-29 | 中国科学院山西煤炭化学研究所 | Method for improving water resistance or solvent resistance of waterborne polyurethane |
| CN111057200B (en) * | 2019-12-02 | 2021-12-24 | 中昊北方涂料工业研究设计院有限公司 | Polyurethane elastic resin containing diaminodiphenyl ether structural unit |
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