CN1350021A - Semi-crystalline dendritic polyether amide oligomer capable of being radiation cured and its prepn - Google Patents
Semi-crystalline dendritic polyether amide oligomer capable of being radiation cured and its prepn Download PDFInfo
- Publication number
- CN1350021A CN1350021A CN 00119066 CN00119066A CN1350021A CN 1350021 A CN1350021 A CN 1350021A CN 00119066 CN00119066 CN 00119066 CN 00119066 A CN00119066 A CN 00119066A CN 1350021 A CN1350021 A CN 1350021A
- Authority
- CN
- China
- Prior art keywords
- reaction
- unsaturated
- alcohol
- polyether amide
- acid
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
Landscapes
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Polyethers (AREA)
- Macromonomer-Based Addition Polymer (AREA)
Abstract
The present invention relates to a radiation-curable semi-crystalline dendrite polyether amide oligomer and its preparation method. It is characterized by that on the basis of synthesis of dendrite polyether amide it adopts "two-step process" or "three-step process" to make modification to form methacrylic acid and/or acrylic acid double bond and long carbochain whose contained carbon atomicity is greater than 10 or benzene ring on its terminal group. The obtained oligomer is low in melt viscosity, and its viscosity can be quickly reduced, so that it is favorable for levelling, and convenient for spray coating process.
Description
The present invention relates to polyether amide oligomer that can be applicable to radiation curable powder coating and preparation method thereof.
Powder coating is not owing to contain any solvent, and no organic volatile composition no matter from environment or economic angle, all is a very advantageous.But traditional thermofixation powder coating can't be applied to heat sensitivity materials such as timber, plastics and medium-density plate because solidification value is higher.Radiation curable powder coating separates fusion with solidification process, powder is earlier at 100 ℃ of left and right sides fusion levellings, then with UV-light or electrocuring, avoided the infringement of comparatively high temps to material, make powder coating can be applied to the heat sensitivity material, and can save energy, shorten the production cycle.The oligomerisation that exploitation can be applicable to radiation curable powder coating embodies the focus that has become paint field.
U.S. Pat 5068305 has been reported the solid oligomer that can be used for heat or high-energy radiation powder coating, pure and mild 2-20 part of list of containing (methyl) acrylic acid groups by the organic list of 40-80 part or polyisocyanates and 15-20 part is contained isocyanate reacting group but is not contained the compound reaction of (methyl) acrylic acid groups, (methyl) acrylic double bond that obtains having 3-10%, at 50-180 ℃ of fused urethane.But the melting viscosity of this oligomer is higher, and curing speed is slower.
U.S. Pat 6001428 has been reported the solid epoxy oligomer of uV curable, is higher than 35 ℃ cationic polymerizable polyglycidyl ether or many glycidyl esters and liquid state or single, double, the many Resins, epoxy of crystalline or ring acetal by second-order transition temperature and forms.But the cost of positively charged ion ultraviolet light polymerization is higher, and curing speed is slower, and the melting viscosity of this oligomer is also higher.
U.S. Pat 5935661 and US 5789039 have reported the solid oligomer of radiation-curable, particularly ultraviolet curable, mainly form, comprise bisphenol type, phenol aldehyde modified bisphenol type and aliphatics type (comprising Hydrogenated Bisphenol A type, methyl propenoic acid glycidyl ether type and vinylformic acid glycidyl ether type) Resins, epoxy by positively charged ion catalytic resin, particularly Resins, epoxy.This oligomer need add other auxiliary agents at 100 ℃ of levellings, can be coated with to be contained on the thermo-sensitivity base material.The cationic radiation-curing cost is higher, curing speed is slow, the higher shortcoming of oligomer melting viscosity but exist equally.
U.S.'s " macromole " " Macromolecules " (1991 the 24th volumes, the 1443-1444 page or leaf) and China " chemical journal " (1997 the 55th the volume, the 595-599 page or leaf) reported the synthetic method of the dendritic polyether amide of different end group respectively, but adopting the resulting dendritic polyether amide of this method is unbodied polymkeric substance, and do not contain methacrylic acid or acrylic-functional, therefore can't radiation curing.
Traditional radiation-curable solid oligomer mostly is the higher linear amorphous polymer of second-order transition temperature, has higher melting viscosity, viscosity reduces slowlyer when temperature is higher than second-order transition temperature, thereby levelling is difficult, and its lower functional group content makes its radiation curing speed slower.
The present invention proposes a kind of semi-crystalline dendritic polyether amide oligomer that can be applicable to radiation curable powder coating and preparation method thereof, to overcome the above-mentioned defective of prior art.
The preparation method of radiation-curable semi-crystalline dendritic polyether amide oligomer of the present invention is " nuclear " with the multifunctional molecule polyvalent alcohol, adds vinyl cyanide in the presence of the organic basic catalyzer, under agitation 5-25 ℃ was reacted 6-10 hour, neutralization, extraction obtains polynitriles after the underpressure distillation; Add monohydroxy-alcohol then in the presence of an acidic catalyst, under agitation 75-100 ℃ was reacted 10-14 hour, neutralization, and extraction obtains polynary ester after the underpressure distillation; Add polyhydroxy amine at last in the presence of basic catalyst, under agitation 20-50 ℃ was reacted 30-60 hour, filtered, and filtrate except that after desolvating, obtains the terminal hydroxy group dendritic polyether amide through underpressure distillation;
It is characterized in that: with the above-mentioned terminal hydroxy group dendritic polyether amide for preparing is raw material, " " or " three-step approach " carries out modification to two step method in employing, make on its end group to form methacrylic acid and/or acrylic double bond and carbon atom quantity, promptly obtain the radiation-curable semi-crystalline dendritic polyether amide oligomer greater than 10 long carbochain or phenyl ring.
The multifunctional molecule polyvalent alcohol of described conduct " nuclear ", its chemical formula can be expressed as R (OH)
m, R is the alkyl or aryl that contains 1-12 carbon in the formula, m is more than or equal to 2; This multifunctional molecule polyvalent alcohol comprises dibasic alcohol, trivalent alcohol, tetravalent alcohol or other polyvalent alcohols; Wherein dibasic alcohol comprises aliphatic dihydroxy alcohol, alicyclic dibasic alcohol or aromatic diol; Aliphatic dihydroxy alcohol comprises 1, ammediol, 1,2-ethylene glycol, 1, the 4-butyleneglycol, 1, the 5-pentanediol, 1, the 6-hexylene glycol, dihydroxy methylpropane, 1,1-dimethyl-1, ammediol, 2-propyl group-2-methyl isophthalic acid, ammediol, 2-butyl-2-ethyl-1, ammediol, 2,2-diethyl-1, ammediol, 1, the 2-propylene glycol, 1, the 3-butyleneglycol, 2,2,4-trimethylammonium-1,3-pentanediol, trimethylammonium-1, the 6-hexylene glycol, the 2-methyl isophthalic acid, ammediol, one two (ethylene glycol) that contract, two three (ethylene glycol) that contract, polyoxyethylene glycol, one two (propylene glycol) that contract, two three (propylene glycol) or the polypropylene glycols that contract; Alicyclic dibasic alcohol comprises cyclohexanedimethanol or ring formaldehyde dimethyl acetal; Aromatic diol comprises 1,4-xylylene dicarbaldehyde or 1-phenyl-1; Described trivalent alcohol comprises TriMethylolPropane(TMP), trimethylolethane, tri hydroxy methyl butane, 3,5,5-trimethylammonium-2,2-dihydroxymethyl-1-hexanol, glycerol or 1,2,6-hexanetriol; Described tetravalent alcohol comprises tetramethylolmethane, contract TriMethylolPropane(TMP), glycol ether, contract trimethylolethane and other alicyclic or aromatic series tetravalent alcohol; Described polyvalent alcohol such as dipentaerythritol.
Described organic basic catalyzer comprises organic hydroxide amine catalyst such as tetraethyl-oxyammonia, phenyl trimethylammonium oxyammonia or pure sodium catalyst such as sodium methylate, sodium ethylate.
Described acid catalyst comprises sulfuric acid, tosic acid or sulfonate resin.
Described monohydroxy-alcohol, its chemical formula can be expressed as ROH, and R is the alkyl or aryl of 1-12 carbon, and this monohydroxy-alcohol comprises methyl alcohol, ethanol, propyl alcohol, butanols or phenylcarbinol.
The used suitable solvent of described extraction comprises ether, methylene dichloride, chloroform, toluene or ethyl acetate.
Described basic catalyst comprises metal salt catalyst such as salt of wormwood, Quilonum Retard or pure sodium catalyst such as sodium methylate, sodium ethylate.
Described polyhydroxy amine, its chemical formula can be expressed as R
1(H) NR
2(R
3OH)
m, R in the formula
1Be the alkyl or aryl of H or 1-12 carbon, R
2, R
3Be the alkyl or aryl of 1-12 carbon, m is 2 or 3; This poly-hydroxy replaces monoamine or diamine comprises diethanolamine, dipropanolamine, two butanolamines, diamyl hydramine, N, N-dihydroxyphenyl ethyl-3-amine, dihydroxymethyl ethylamine or tri methylol amino methane.
Described " two step method " modification, that is: the first step, with the terminal hydroxy group dendritic polyether amide slowly be added dropwise to while stirring with the hydroxyl equimolar amount contain can with the unsaturated end-caps (I) of the functional group of hydroxyl reaction, in the presence of catalyzer and stopper, 80-120 ℃ of reaction 5-8 hour; Second step, the product of gained is dissolved in the solvent, slowly be added dropwise to while stirring the pendant hydroxyl group equimolar amount that generates with the first step reaction and contain can with the functional group of hydroxyl reaction and carbon atom quantity greater than 10 the long carbochain or the compound of phenyl ring, in the presence of catalyzer, 30-70 ℃ was reacted 10-30 hour, and removed by product with acetone and water washing successively;
Described the first step catalysts comprises the metallic tin compound, and consumption is 0.5-2wt%, or tertiary amine, and consumption is 1-3wt%; The described second step catalysts comprises the metallic tin compound, and consumption is 0.5-2wt%;
The first step reaction suitable reaction temperature is 80-120 ℃, and the reaction times is 5-8 hour; Second step reaction suitable reaction temperature is 30-70 ℃, and the reaction times is 10-30 hour.
Described " three-step approach " modification, that is: the first step, with the terminal hydroxy group dendritic polyether amide slowly be added dropwise to while stirring with the hydroxyl equimolar amount, contain can with the unsaturated end-caps (I) of the functional group of hydroxyl reaction, in the presence of catalyzer and stopper, 80-120 ℃ of reaction 5-8 hour; Second step, the product of gained is dissolved in the solvent, slowly be added dropwise to the unsaturated end-caps (II) that contains the functional group that to react with the pendant hydroxyl group that the first step reaction generates while stirring by a certain percentage, in the presence of catalyzer and stopper, 20-140 ℃ was reacted 6-30 hour, and extraction process is removed the byproduct of generation; The 3rd step, the product of gained is dissolved in the solvent, slowly be added dropwise to while stirring with remaining pendant hydroxyl group equimolar amount of second step and contain can with the functional group of hydroxyl reaction and carbonatoms greater than 10 the long carbochain or the compound of phenyl ring, in the presence of catalyzer, 30-70 ℃ was reacted 10-30 hour, and removed by product with acetone and water washing successively;
Described " certain proportion " is meant the molar reactive proportioning between the pendant hydroxyl group that the reaction of unsaturated end-caps (II) and the first step generates, and represents that with X its value is 0＜X＜1;
Described containing can comprise unsaturated monocarboxylic acid acid anhydride, unsaturated monocarboxylic acid, unsaturated acyl chlorides or unsaturated isocyanate with the unsaturated end-caps (II) of the functional group of hydroxyl reaction; Described unsaturated monocarboxylic acid acid anhydride comprises acrylic anhydride or methacrylic anhydride; Described unsaturated monocarboxylic acid comprises acrylic or methacrylic acid; Described unsaturated acyl chlorides comprises acrylate chloride or methacrylic chloride; Described unsaturated isocyanate comprises vinyl toluene isocyanic ester, Jia Jibingxisuanyizhi isocyanic ester or by the unsaturated isocyanate of saturated vulcabond and 1/2 normal unsaturated oxy-compound prepared in reaction; Wherein saturated vulcabond comprises tolylene diisocyanate, HDI, phenylbenzene methylene isocyanic ester or isophorone diisocyanate; Unsaturated oxy-compound comprises Hydroxyethyl acrylate, hydroxyethyl methylacrylate or tridecylene alcohol;
Described the first step catalysts comprises the metallic tin compound, and consumption is 0.5-2wt%, or tertiary amine, and consumption is 1-3wt%; The described second step catalysts comprises tertiary amine or metallic tin compound, and consumption is 0.5-2wt%; Described three-step reaction catalyzer comprises the metallic tin compound, and consumption is 0.5-2wt%;
The first step reaction suitable reaction temperature is 80-120 ℃, and the reaction times is 5-8 hour;
The second step reaction is if use unsaturated acid anhydride, unsaturated acyl chlorides or unsaturated isocyanate modification, and temperature of reaction was good with 20-50 ℃, reaction times with 18-30 hour; If use monocarboxylic acid, temperature of reaction was good with 80-140 ℃, reaction times with 6-20 hour;
The three-step reaction suitable reaction temperature is 30-70 ℃, and the reaction times is 10-30 hour.
It is above-mentioned that " " or in " three-step approach ", described containing can comprise unsaturated epoxy compound such as glycidyl acrylate or glycidyl methacrylate with the unsaturated end-caps (I) of the functional group of hydroxyl reaction to two step method;
Described metallic tin compound comprises tin tetrachloride, tin protochloride, dibutyl tin protoxide or dibutyl tin laurate;
Described tertiary amine comprises xylidine, dimethyl benzylamine, dimethyl aminopyridine or dimethylethanolamine;
Described stopper comprises MEHQ or Resorcinol, and consumption is 500-4000ppm;
Described solvent comprises methylene dichloride, ether, ethyl acetate, toluene, chloroform or N-Methyl pyrrolidone;
Described containing can comprise monobasic acyl chlorides, monobasic isocyanic ester or monocarboxylic acid greater than 10 the long carbochain or the compound of phenyl ring with the functional group of hydroxyl reaction and carbon atom quantity; Monobasic acyl chlorides wherein, its chemical formula can be expressed as RCOCl, and R is the alkyl or aryl greater than 10 carbon in the formula, and this monobasic acyl chlorides comprises undecanoyl chlorine, lauroyl chloride, myristyl chloride, hexadecanoyl chloride or Benzoyl chloride; Monobasic isocyanic ester wherein, its chemical formula can be expressed as RNCO, and R is the alkyl or aryl greater than 10 carbon in the formula, and this monobasic isocyanic ester comprises ten vulcabond, ten tetraisocyanates, 16 isocyanic ester, 18 isocyanic ester or benzene isocyanic ester; Monocarboxylic acid wherein, its chemical formula can be expressed as RCOOH, and R is the alkyl or aryl greater than 10 carbon in the formula, and this monocarboxylic acid comprises undecanoic acid, stearic acid, Palmiticacid or phenylformic acid.
The present invention can be applicable to the radiation-curable semi-crystalline dendritic polyether amide oligomer of radiation curable powder coating, it is characterized in that on the basis of synthetic dendritic polyether amide, adopt that above-mentioned " " or " three-step approach " carry out methacrylic acid and/or acrylated modification and long carbochain or phenyl ring modification to two step method, makes to form methacrylic acid and/or acrylic double bond and carbon atom quantity on its end group and obtain greater than 10 long carbochain or phenyl ring.
Because synthetic dendritic polyether amide of the present invention is a kind of highly branched polymkeric substance, intermolecular have less chain around, compare with the linear polymer in 5789039 with United States Patent (USP) 5068305,6001428,5935661, have lower melting viscosity; And oligomer of the present invention is a kind of hemicrystalline polymkeric substance, compare with the amorphous polymer in the above-mentioned United States Patent (USP), when temperature the viscosity degradation more than the fusing point than amorphous polymer when the viscosity degradation of temperature more than second-order transition temperature faster.So radiation-curable semi-crystalline dendritic polyether amide oligomer of the present invention is more conducive to levelling, the spraying operation is more prone to.
Because synthetic dendritic polyether amide of the present invention has numerous terminal hydroxy groups, through after the modification, has numerous activity double keys, compare with the linear polymer in 5789039 with United States Patent (USP) 5068305,6001428,5935661, radiation curing speed is faster, so just improve production efficiency greatly, saved the energy, be easier to suitability for industrialized production.The present invention is first on the basis of synthetic dendritic polyether amide, " " or " three-step approach " carries out the modification of (methyl) acrylated and long carbochain or phenyl ring modification to two step method in employing, make on its end group and to form methacrylic acid and/or acrylic double bond and carbon atom quantity greater than 10 long carbochain or phenyl ring, thereby can be applicable to radiation curable powder coating, have wide prospect in industrial application.
Further describe the mensuration of preparation method, radiation curing and the crystal property of radiation-curable semi-crystalline dendritic polyether amide oligomer of the present invention by the following examples.But the present invention is not limited to listed embodiment.
The preparation of embodiment 1 terminal hydroxy group dendritic polyether amide
1, the preparation of polynitriles
At the capacity that mechanical stirring device is housed is in the three-necked bottle of 3L, adds 1L distilled water, 136g (1mol) tetramethylolmethane, and the 60ml weight concentration is 25% the tetraethyl-oxyammonia aqueous solution and 462ml (7mol) vinyl cyanide; Maintain the temperature at 12 ℃, stir reaction down 8 hours fast; Reaction solution is transferred in the separating funnel of 5L, add in the 15ml concentrated hydrochloric acid and after, tell following oil reservoir and dissolve in the 1.5L toluene, with 250ml distilled water wash twice, underpressure distillation obtains colourless oil liquid after removing toluene and a spot of water; It is in 9: 1 water and the mixed liquid of alcoholic acid that the colourless oil liquid of gained is dissolved in 3250-3350ml ebullient volume ratio, slowly be cooled to 25 ℃ under the mechanical stirring, again with after the ice-water bath cooling, with gained crystal Vanadium Pentoxide in FLAKES drying under reduced pressure, obtain white needle-like crystals 261g, productive rate is 75%, and fusing point is 44-46 ℃.
Products therefrom is through Infrared spectroscopy, at 2251cm
-1The itrile group charateristic avsorption band at place, 1114cm
-1And 1073cm
-1The carbon oxygen carbon charateristic avsorption band at place all occurs, and former 3400-3100cm
-1The tetramethylolmethane hydroxyl charateristic avsorption band and the 1600cm at place
-1And 969cm
-1The vinyl cyanide carbon-carbon double bond charateristic avsorption band at place all disappears.
Products therefrom is that solvent is through the hydrogen nuclear magnetic resonance spectrum analysis with the deuterochloroform, 2.61ppm the triplet of locating belongs to the hydrogen atom near the methylene radical of itrile group, 3.48ppm the singlet of locating belongs to the hydrogen atom near the methylene radical of quaternary carbon atom, the triplet at 3.66ppm place belongs to the hydrogen atom near the methylene radical of Sauerstoffatom.
Through above-mentioned analysis as can be known, above-mentioned product is the quaternary nitrile.
Following table has been listed the productive rate and the color of reaction different time products therefrom under differing temps:
| Temperature of reaction (℃) | Reaction times (h) | Productive rate (%) | The product color |
| ????5 | ????10 | ????70 | White |
| ????15 | ????8 | ????75 | White |
| ????25 | ????6 | ????65 | Little Huang |
If the tetramethylolmethane with in alternative this example of polyvalent alcohols such as glycerine, TriMethylolPropane(TMP) also all can obtain polynitriles.
2, the preparation of polynary ester cooling is added dropwise to the 30ml vitriol oil in the 70ml dehydrated alcohol down carefully, be in the 250ml three-necked bottle with the mixed solution capacity of being transferred to then, the quaternary nitrile that adds the above-mentioned preparation of 16g (0.046mol), in 85 ℃ of reactions 12 hours, with the reaction solution concentrating under reduced pressure, concentrated solution was poured in 70 frozen water, use ethyl acetate extraction, organic layer washs with 5% sodium carbonate solution, and dry back concentrating under reduced pressure obtains 16.5g yellow oily liquid, and productive rate is 68%.
Products therefrom is through Infrared spectroscopy, at 1732cm
-1The ester group charateristic avsorption band at place occurs, and former 2251cm
-1The itrile group charateristic avsorption band at place disappears.
Products therefrom is that solvent is through the hydrogen nuclear magnetic resonance spectrum analysis with the deuterochloroform, 1.26ppm the triplet of locating belongs to the hydrogen atom of terminal methyl group, 2.53ppm the triplet of locating belongs to the hydrogen atom near the methylene radical of carbonyl, 3.34ppm the singlet of locating belongs to the hydrogen atom near the methylene radical of carbonyl, 3.64ppm the triplet of locating belongs to the hydrogen atom near the methylene radical of ehter bond Sauerstoffatom, 4.10 and the quartet at 4.18ppm place belong to the hydrogen atom of the methylene radical in the terminal ethyl.
Through above-mentioned analysis as can be known, this routine product is the quaternary ester.
Following table has been listed the productive rate and the color of reaction different time products therefrom under differing temps:
| Temperature of reaction (℃) | Reaction times (h) | Productive rate (%) | The product color |
| ????70 | ????14 | ????65 | Yellow |
| ????85 | ????12 | ????68 | Yellow |
| ????100 | ????10 | ????60 | Deep yellow |
Other polynitriles all can obtain polynary ester through above-mentioned reaction process.
3, the preparation of terminal hydroxy group dendritic polyether amide
The quaternary ester that in capacity is the three-necked bottle of 250ml, adds 13.6g (0.112mol) tri methylol amino methane, the above-mentioned preparation of 15g (0.028mol), 17g (0.123mol) Anhydrous potassium carbonate and 70ml dimethyl sulfoxide (DMSO), stir down in 25 ℃ of reactions 12 hours, then in 40 ℃ of reactions 40 hours; With reacting liquid filtering, insolubles is concentrated filtrate with the washing of 10ml dimethyl sulfoxide (DMSO), and underpressure distillation obtains the little yellow high viscosity liquid of 21.8g, and productive rate is 93%.
Products therefrom is through Infrared spectroscopy, 3383 and 1046cm
-1The hydroxyl charateristic avsorption band at place, 1650 and 1566cm
-1The acid amides charateristic avsorption band at place all occurs, and former 1732cm
-1The ester group charateristic avsorption band at place disappears.
Products therefrom is that solvent is through the hydrogen nuclear magnetic resonance spectrum analysis with deuterium for water, 2.42ppm the triplet of locating belongs to the hydrogen atom near the methylene radical of amido linkage, 3.49ppm the triplet of locating belongs to the hydrogen atom near the methylene radical of ehter bond Sauerstoffatom, 4.18ppm the singlet of locating belongs to the hydrogen atom near the methylene radical of quaternary carbon atom, the singlet at 4.7ppm place belongs to the hydrogen atom near the methylene radical of last terminal hydroxy group.
Products therefrom is that solvent is through the carbon-13 nmr spectra analysis with deuterium for water, 175.75ppm the peak of locating belongs to the carbon atom of amido linkage, 70.32ppm the peak of locating belongs to the carbon atom near the center quaternary carbon atom, 63.88ppm the peak of locating belongs to the carbon atom near the ehter bond Sauerstoffatom, 62.58ppm the peak of locating belongs to terminal quaternary carbon atom, 56.92ppm the peak of locating belongs to the carbon atom near terminal quaternary carbon atom, 40.26ppm the peak of locating belongs near the center quaternary carbon atom, the peak at 32.94ppm place belongs to the carbon atom near carbonyl.
Products therefrom is measured through the gas-phase permeation platen press, and molecular weight is 750, and its theoretical molecular is 836.
Through above-mentioned analysis as can be known, in the present embodiment reaction carry out according to anticipation, product should be contain ehter bond and amido linkage the four directions to highly branched polymkeric substance, be called the terminal hydroxy group dendritic polyether amide.
Products therefrom since 185 ℃ of obvious weightlessness, when temperature reaches 338 ℃ of weightlessness 62%, continues weightlessness 26.5% when temperature reaches 800 ℃ through thermogravimetric analysis, still has 11.45% remnants this moment.
Following table has been listed present embodiment reacts the different time products therefrom under differing temps productive rate and color:
| Temperature of reaction (℃) | Reaction times (h) | Productive rate (%) | The product color |
| ????25 | ????60 | ????90 | Yellowish |
| ????25-40 | ????50 | ????93 | Yellowish |
| ????40-50 | ????48 | ????95 | Yellow |
Other polynary esters all can obtain the terminal hydroxy group dendritic polyether amide through the reaction process of present embodiment.
Embodiment 2, the synthetic radiation-curable semi-crystalline dendritic polyether amide of employing " two step method "
The first step: the preparation of methacrylic acidifying dendritic polyether amide
The terminal hydroxy group dendritic polyether amide that in the 250ml three-necked bottle of prolong, dropping funnel and mechanical stirring device is housed, adds preparation among 8.36g (0.01mol) embodiment 1,0.025g (0.071mmol) tin tetrachloride and 0.05g (0.403mmol) MEHQ; 17.95g (0.126mol) methyl propenoic acid glycidyl ether slowly is added dropwise in the three-necked bottle that has been heated to 100 ℃, stirs reaction down 6 hours, obtain the yellow thick liquid of 25g.Productive rate is 95%.
Products therefrom is through Infrared spectroscopy, at 1719cm
-1The carbonyl charateristic avsorption band at place, 1637 and 815cm
-1The two key charateristic avsorption bands of the methacrylic acid at place all occur.
Through above-mentioned analysis as can be known, above-mentioned product is a methacrylic acidifying dendritic polyether amide.
Following table has been listed the productive rate and the color of reaction different time products therefrom under differing temps:
| Temperature of reaction (℃) | Reaction times (h) | Productive rate (%) | The product color |
| ????80 | ????8 | ????92 | Faint yellow |
| ????100 | ????6 | ????95 | Yellow |
| ????120 | ????5 | ????91 | Deep yellow |
Second step: the preparation of hypocrystalline methacrylic acidifying dendritic polyether amide
In being housed, the 250ml three-necked bottle of prolong, dropping funnel and mechanical stirring device adds the methacrylic acidifying dendritic polyether amide, 10ml methylene dichloride and 4ml (3mmol) triethylamine that prepare in 5.1g (2mmol) previous step, 7.1g (24mmol) 18 isocyanic ester are dissolved in the 20ml anhydrous propanone, under room temperature, stirring, slowly be added dropwise in the three-necked bottle, be warming up to 50 ℃ of reactions 20 hours then; With the reaction solution decompress filter, after the gained solid is removed by product with acetone and water washing successively, grind, behind the drying under reduced pressure, obtain the 7.2g white powder.Productive rate is 75.4%.
Products therefrom is through Infrared spectroscopy, at 3320cm
-1The nitrogen hydrogen charateristic avsorption band at place, 1641 and 1543cm
-1Amido linkage charateristic avsorption band, the 716cm at place
-1The long carbochain methylene radical charateristic avsorption band charateristic avsorption band at place all occurs, and 2275cm
-1The isocyanic ester charateristic avsorption band at place disappears.
Products therefrom is analyzed with D/MAX-YA anode X-ray diffractometer, finds that from spectrogram there are several tangible peak crystallization at tangible non-crystalline region and 2 θ angles between 2 °-20 °.
Through above-mentioned analysis as can be known, above-mentioned product is a methacrylic acidifying dendroid hypocrystalline polyetheramides.
Following table has been listed present embodiment reacts the different time products therefrom under differing temps productive rate and color:
| Temperature of reaction (℃) | Reaction times (h) | Productive rate (%) | The product color |
| ????30 | ????30 | ????68 | White |
| ????50 | ????20 | ????75 | White |
| ????70 | ????10 | ????75 | Little Huang |
Embodiment 3, the synthetic radiation-curable semi-crystalline dendritic polyether amide of employing " three-step approach "
The first step: the preparation of methacrylic acidifying dendritic polyether amide, reaction process is described identical with the first step among the embodiment 2.
Second step: the preparation of methacrylic acidifying and part propylene acidifying dendritic polyether amide
In being housed, the 250ml three-necked bottle of dropping funnel and mechanical stirring device adds the methacrylic acidifying dendritic polyether amide, 30ml methylene dichloride and 20ml (0.012mol) triethylamine that prepare in the above-mentioned the first step of 25.46g (0.01mol), and three-necked bottle placed ice-water bath, stir down, with 3.9ml (0.048mol, be the hydroxyl mole number 40%) acrylate chloride slowly be added dropwise to, kept room temperature reaction 24 hours; Reaction solution is with the hydrogen chloride solution of 1 volumetric molar concentration, 10% sodium hydrogen carbonate solution and distilled water extracting twice respectively successively, organic layer with anhydrous magnesium sulfate drying after, filter, remove methylene dichloride after, obtain the yellow thick liquid of 24g.Productive rate is 85%.
Products therefrom is through Infrared spectroscopy, at 809cm
-1The acrylic double bond charateristic avsorption band at place occurs.
Through above-mentioned analysis as can be known, above-mentioned product is methacrylic acidifying and part propylene acidifying dendritic polyether amide.
Following table has been listed the productive rate and the color of reaction different time products therefrom under differing temps:
| Temperature of reaction (℃) | Reaction times (h) | Productive rate (%) | The product color |
| ????20 | ????30 | ????83 | Yellow |
| ????30 | ????24 | ????85 | Yellow |
| ????50 | ????18 | ????84 | Pale brown look |
The 3rd step: the preparation of acidifying of hypocrystalline methacrylic and part propylene acidifying dendritic polyether amide
The methacrylic acidifying and part propylene acidifying dendritic polyether amide, 10ml methylene dichloride and 4ml (3mmol) triethylamine that in the 250ml three-necked bottle of prolong, dropping funnel and mechanical stirring device is housed, add 5.6g (2mmol) preparation in above-mentioned second step, with 4.62g (15.6mmol, 1.08 times of residual hydroxyl mole number) 18 isocyanic ester are dissolved in the 10ml anhydrous propanone, under room temperature, stirring, slowly be added dropwise in the three-necked bottle, be warming up to 50 ℃ of reactions 20 hours then; With the reaction solution decompress filter, after the gained solid is removed by product with acetone and water washing successively, grind, behind the drying under reduced pressure, obtain the 7.9g white powder.Productive rate is 77.3%.
Products therefrom is through Infrared spectroscopy, at 3342cm
-1The nitrogen hydrogen charateristic avsorption band at place, 1615 and 1573cm
-1Amido linkage charateristic avsorption band, the 716cm at place
-1The long carbochain methylene radical charateristic avsorption band at place all occurs, and 2275cm
-1The isocyanic ester charateristic avsorption band at place disappears.
Products therefrom finds that from spectrogram there are several tangible peak crystallization at tangible non-crystalline region and 2 θ angles with D/MAX-YA anode X light diffracting analysis between 2 °-20 °.
Through above-mentioned analysis as can be known, above-mentioned product is methacrylic acidifying and part propylene acidifying ingotism polyetheramides.
Following table has been listed present embodiment reacts the different time products therefrom under differing temps productive rate and color:
| Temperature of reaction (℃) | Reaction times (h) | Productive rate (%) | The product color |
| ??30 | ??30 | ??68 | White |
| ??50 | ??20 | ??75 | White |
| ??70 | ??10 | ??75 | Little Huang |
The crystal property test of embodiment 4, radiation-curable semi-crystalline dendritic polyether amide
1, the mensuration of the fusing point of radiation-curable semi-crystalline dendritic polyether amide and second-order transition temperature
Fusing point and second-order transition temperature with the semi-crystalline dendritic polyether amide of preparation among differential scanning calorimeter Shimadzu DSC-50 mensuration embodiment 2 and the embodiment 3 the results are shown in following table:
| Fusing point (℃) | Second-order transition temperature (℃) | |
| Embodiment 2 samples | ???115.21 | ???75.29 |
| Embodiment 3 samples | ???116.06 | ???74.16 |
As seen from the above table, the semi-crystalline dendritic polyether amide of embodiment 2 and embodiment 3 preparations has lower fusing point and high glass transition.Lower fusing point can make them be painted on the heat sensitivity materials such as timber, plastics and medium-density plate; And high glass transition can make them be easy to store.
The radiation curing of embodiment 5 semi-crystalline dendritic polyether amides and curing membrane performance test
1, the not sticking time of the mensuration of the not sticking time of the radiation curing of semi-crystalline dendritic polyether amide and cured film is meant that irradiation coating makes its not sticking fully needed time.
Get each 5g of semi-crystalline dendritic polyether amide of embodiment 2 and embodiment 3 preparations respectively; mix with light trigger 1-hydroxy-cyclohexyl methyl phenyl ketone (Igarcure 184) 200mg (4wt%); be stirred to evenly; be heated to the film of painting 100 micron thickness on 120 ℃ the sheet glass with spreader; sample places 10 centimetres of lamps apart from the place; under nitrogen protection, with PhilipHPM-15 1000W ultraviolet lamp (UV) irradiation different time.With the 200g counterweight one cotton balls was pressed in coatingsurface behind the uv irradiation after 30 seconds, observes the surface and whether adhere to cotton.If surface not sticking cotton, then this irradiation time time of cannot not being sticking.The results are shown in following table:
| Embodiment 2 samples | Embodiment 3 samples | |
| The not sticking time (second) | ??20 | ??15 |
This shows that semi-crystalline dendritic polyether amide of the present invention can be at room temperature with ultraviolet light irradiation fast setting film forming, therefore can enhance productivity greatly and save the energy, and be easy to suitability for industrialized production.
2, the mensuration of the pendulum hardness of cured film
Get each 5g of semi-crystalline dendritic polyether amide of embodiment 2 and embodiment 3 preparations respectively; mix to evenly with light trigger 1-hydroxy-cyclohexyl methyl phenyl ketone (Irgacure 184) 200mg (4wt%); be heated to the film of painting 75 micron thickness on 120 ℃ the sheet glass with spreader; sample places 10 centimetres of lamps apart from the place; under nitrogen protection; with Philip HPM-151000W ultraviolet lamp (UV) irradiation, measure required time.The QBY type pendulum-type sclerometer made from Tianjin instrument plant is tested the pendulum hardness of its cured film, and the result is as follows:
The pendulum hardness of the cured film of embodiment 2 specimen preparations
| Irradiation time (second) | ??20 | ??25 | ??30 |
| Pendulum hardness (second) | ??217 | ??249 | ??252 |
The pendulum hardness of the cured film of embodiment 3 specimen preparations
| Irradiation time (second) | ????15 | ????20 | ????30 |
| Pendulum hardness (second) | ????220 | ????304 | ????310 |
By above-mentioned two tables as seen, after the radiation-curable semi-crystalline dendritic polyether amide ultra-violet curing film forming of the present invention, cured film has certain rigidity, meets industrial application requirements.
3, the mensuration of the thermostability of cured film
Measure in the mensuration of above-mentioned cured film pendulum hardness the thermostability of two kinds of cured film when irradiation time is 30 seconds with thermal gravimetric analyzer Shimadzu TGA-50H, the result is as follows:
The thermostability of the cured film of embodiment 2 specimen preparations
| Temperature (℃) | ????241.94 | ????381.43 | ????499.237 |
| Weightless (%) | Beginning is obviously weightless | ????-77.422 | ????-91.659 |
The thermostability of the cured film of embodiment 3 specimen preparations
| Temperature (℃) | ????250.17 | ????367.17 | ????498.38 |
| Weightless (%) | Beginning is obviously weightless | ????-74.069 | ????-91.425 |
By the listed result of above-mentioned two tables as seen, after the radiation-curable semi-crystalline dendritic polyether amide ultra-violet curing film forming of the present invention, cured film has thermostability preferably, meets industrial application requirements.
Claims (7)
1, a kind of preparation method of radiation-curable semi-crystalline dendritic polyether amide oligomer is " nuclear " with the multifunctional molecule polyvalent alcohol, adds vinyl cyanide in the presence of the organic basic catalyzer, under agitation 5-25 ℃ was reacted 6-10 hour, neutralization, extraction obtains polynitriles after the underpressure distillation; Add monohydroxy-alcohol then in the presence of an acidic catalyst, under agitation 75-100 ℃ was reacted 10-14 hour, neutralization, and extraction obtains polynary ester after the underpressure distillation; Add polyhydroxy amine at last in the presence of basic catalyst, under agitation 20-50 ℃ was reacted 30-60 hour, filtered, and filtrate except that after desolvating, obtains the terminal hydroxy group dendritic polyether amide through underpressure distillation;
It is characterized in that: with the above-mentioned terminal hydroxy group dendritic polyether amide for preparing is raw material, " " or " three-step approach " carries out modification to two step method in employing, make on its end group to form methacrylic acid and/or acrylic double bond and carbon atom quantity, promptly obtain the radiation-curable semi-crystalline dendritic polyether amide oligomer greater than 10 long carbochain or phenyl ring.
2, the preparation method of radiation-curable semi-crystalline dendritic polyether amide oligomer according to claim 1, be characterised in that the multifunctional molecule polyvalent alcohol of described conduct " nuclear ", its chemical formula can be expressed as R (OH) m, and R is the alkyl or aryl that contains 1-12 carbon in the formula, and m is more than or equal to 2; This multifunctional molecule polyvalent alcohol comprises dibasic alcohol, trivalent alcohol, tetravalent alcohol or other polyvalent alcohols; Wherein dibasic alcohol comprises aliphatic dihydroxy alcohol, alicyclic dibasic alcohol or aromatic diol; Aliphatic dihydroxy alcohol comprises 1, ammediol, 1,2-ethylene glycol, 1, the 4-butyleneglycol, 1, the 5-pentanediol, 1, the 6-hexylene glycol, dihydroxy methylpropane, 1,1-dimethyl-1, ammediol, 2-propyl group-2-methyl isophthalic acid, ammediol, 2-butyl-2-ethyl-1, ammediol, 2,2-diethyl-1, ammediol, 1, the 2-propylene glycol, 1, the 3-butyleneglycol, 2,2,4-trimethylammonium-1,3-pentanediol, trimethylammonium-1, the 6-hexylene glycol, the 2-methyl isophthalic acid, ammediol, one two (ethylene glycol) that contract, two three (ethylene glycol) that contract, polyoxyethylene glycol, one two (propylene glycol) that contract, two three (propylene glycol) or the polypropylene glycols that contract; Alicyclic dibasic alcohol comprises cyclohexanedimethanol or ring formaldehyde dimethyl acetal; Aromatic diol comprises 1,4-xylylene dicarbaldehyde or 1-phenyl-1; Described trivalent alcohol comprises TriMethylolPropane(TMP), trimethylolethane, tri hydroxy methyl butane, 3,5,5-trimethylammonium-2,2-dihydroxymethyl-1-hexanol, glycerol or 1,2,6-hexanetriol; Described tetravalent alcohol comprises tetramethylolmethane, contract TriMethylolPropane(TMP), glycol ether, contract trimethylolethane and other alicyclic or aromatic series tetravalent alcohol; Described polyvalent alcohol such as dipentaerythritol.
3, the preparation method of radiation-curable semi-crystalline dendritic polyether amide oligomer according to claim 1 is characterised in that:
Described organic basic catalyzer comprises organic hydroxide amine catalyst such as tetraethyl-oxyammonia, phenyl trimethylammonium oxyammonia or pure sodium catalyst such as sodium methylate, sodium ethylate;
Described acid catalyst comprises sulfuric acid, tosic acid or sulfonate resin;
Described monohydroxy-alcohol, its chemical formula can be expressed as ROH, and R is the alkyl or aryl of 1-12 carbon, and this monohydroxy-alcohol comprises methyl alcohol, ethanol, propyl alcohol, butanols or phenylcarbinol;
The used suitable solvent of described extraction comprises ether, methylene dichloride, chloroform, toluene or ethyl acetate;
Described basic catalyst comprises metal salt catalyst such as salt of wormwood, Quilonum Retard or pure sodium catalyst such as sodium methylate, sodium ethylate;
Described polyhydroxy amine, its chemical formula can be expressed as R1 (H) NR2 (R3OH) m, and R1 is the alkyl or aryl of H or 1-12 carbon in the formula, and R2, R3 are the alkyl or aryl of 1-12 carbon, and m is 2 or 3; This poly-hydroxy replaces monoamine or diamine comprises diethanolamine, dipropanolamine, two butanolamines, diamyl hydramine, N, N-dihydroxyphenyl ethyl-3-amine, dihydroxymethyl ethylamine or tri methylol amino methane.
4, a kind of radiation-curable semi-crystalline dendritic polyether amide oligomer, it is characterized in that on the basis of synthetic dendritic polyether amide, adopt that " " or " three-step approach " carry out methacrylic acid and/or acrylated modification and long carbochain or phenyl ring modification to two step method, makes to form methacrylic acid and/or acrylic double bond and carbon atom quantity on its end group and obtain greater than 10 long carbochain or phenyl ring.
5, as radiation-curable semi-crystalline dendritic polyether amide oligomer as described in claim 1 or 4 and preparation method thereof, be characterised in that described " two step method " modification, that is: the first step, with the terminal hydroxy group dendritic polyether amide slowly be added dropwise to while stirring with the hydroxyl equimolar amount contain can with the unsaturated end-caps (I) of the functional group of hydroxyl reaction, in the presence of catalyzer and stopper, 80-120 ℃ was reacted 5-8 hour; Second step, the product of gained is dissolved in the solvent, slowly be added dropwise to while stirring the pendant hydroxyl group equimolar amount that generates with the first step reaction and contain can with the functional group of hydroxyl reaction and carbon atom quantity greater than 10 the long carbochain or the compound of phenyl ring, in the presence of catalyzer, 30-70 ℃ was reacted 10-30 hour, and removed by product with acetone and water washing successively;
Described the first step catalysts comprises the metallic tin compound, and consumption is 0.5-2wt%, or tertiary amine, and consumption is 1-3wt%; The described second step catalysts comprises the metallic tin compound, and consumption is 0.5-2wt%;
The first step reaction suitable reaction temperature is 80-120 ℃, and the reaction times is 5-8 hour; Second step reaction suitable reaction temperature is 30-70 ℃, and the reaction times is 10-30 hour.
6, as radiation-curable semi-crystalline dendritic polyether amide oligomer as described in claim 1 or 4 and preparation method thereof, be characterised in that described " three-step approach " modification, that is: the first step, with the terminal hydroxy group dendritic polyether amide slowly be added dropwise to while stirring with the hydroxyl equimolar amount, contain can with the unsaturated end-caps (I) of the functional group of hydroxyl reaction, in the presence of catalyzer and stopper, 80-120 ℃ was reacted 5-8 hour; Second step, the product of gained is dissolved in the solvent, slowly be added dropwise to the unsaturated end-caps (II) that contains the functional group that to react with the pendant hydroxyl group that the first step reaction generates while stirring by a certain percentage, in the presence of catalyzer and stopper, 20-140 ℃ was reacted 6-30 hour, and extraction process is removed the byproduct of generation; The 3rd step, the product of gained is dissolved in the solvent, slowly be added dropwise to while stirring with remaining pendant hydroxyl group equimolar amount of second step and contain can with the functional group of hydroxyl reaction and carbonatoms greater than 10 the long carbochain or the compound of phenyl ring, in the presence of catalyzer, 30-70 ℃ was reacted 10-30 hour, and removed by product with acetone and water washing successively;
Described " certain proportion " is meant the molar reactive proportioning between the pendant hydroxyl group that the reaction of unsaturated end-caps (II) and the first step generates, and represents that with X its value is 0＜X＜1;
Described containing can comprise unsaturated monocarboxylic acid acid anhydride, unsaturated monocarboxylic acid, unsaturated acyl chlorides or unsaturated isocyanate with the unsaturated end-caps (II) of the functional group of hydroxyl reaction; Described unsaturated monocarboxylic acid acid anhydride comprises acrylic anhydride or methacrylic anhydride; Described unsaturated monocarboxylic acid comprises acrylic or methacrylic acid; Described unsaturated acyl chlorides comprises acrylate chloride or methacrylic chloride; Described unsaturated isocyanate comprises vinyl toluene isocyanic ester, Jia Jibingxisuanyizhi isocyanic ester or by the unsaturated isocyanate of saturated vulcabond and 1/2 normal unsaturated oxy-compound prepared in reaction; Wherein saturated vulcabond comprises tolylene diisocyanate, HDI, phenylbenzene methylene isocyanic ester or isophorone diisocyanate; Unsaturated oxy-compound comprises Hydroxyethyl acrylate, hydroxyethyl methylacrylate or tridecylene alcohol;
Described the first step catalysts comprises the metallic tin compound, and consumption is 0.5-2wt%, or tertiary amine, and consumption is 1-3wt%; The described second step catalysts comprises tertiary amine or metallic tin compound, and consumption is 0.5-2wt%; Described three-step reaction catalyzer comprises the metallic tin compound, and consumption is 0.5-2wt%;
The first step reaction suitable reaction temperature is 80-120 ℃, and the reaction times is 5-8 hour;
The second step reaction is if use unsaturated acid anhydride, unsaturated acyl chlorides or unsaturated isocyanate modification, and temperature of reaction was good with 20-50 ℃, reaction times with 18-30 hour; If use monocarboxylic acid, temperature of reaction was good with 80-140 ℃, reaction times with 6-20 hour;
The three-step reaction suitable reaction temperature is 30-70 ℃, and the reaction times is 10-30 hour.
7, as radiation-curable semi-crystalline dendritic polyether amide oligomer as described in claim 1 or 4 and preparation method thereof, be characterised in that described " " or in " three-step approach ", described containing can comprise unsaturated epoxy compound such as glycidyl acrylate or glycidyl methacrylate with the unsaturated end-caps (I) of the functional group of hydroxyl reaction to two step method;
Described metallic tin compound comprises tin tetrachloride, tin protochloride, dibutyl tin protoxide or dibutyl tin laurate;
Described tertiary amine comprises xylidine, dimethyl benzylamine, dimethyl aminopyridine or dimethylethanolamine;
Described stopper comprises MEHQ or Resorcinol, and consumption is 500-4000ppm;
Described solvent comprises methylene dichloride, ether, ethyl acetate, toluene, chloroform or N-Methyl pyrrolidone;
Described containing can comprise monobasic acyl chlorides, monobasic isocyanic ester or monocarboxylic acid greater than 10 the long carbochain or the compound of phenyl ring with the functional group of hydroxyl reaction and carbon atom quantity; Monobasic acyl chlorides wherein, its chemical formula can be expressed as RCOC1, and R is the alkyl or aryl greater than 10 carbon in the formula, and this monobasic acyl chlorides comprises undecanoyl chlorine, lauroyl chloride, myristyl chloride, hexadecanoyl chloride or Benzoyl chloride; Monobasic isocyanic ester wherein, its chemical formula can be expressed as RNCO, and R is the alkyl or aryl greater than 10 carbon in the formula, and this monobasic isocyanic ester comprises ten vulcabond, ten tetraisocyanates, 16 isocyanic ester, 18 isocyanic ester or benzene isocyanic ester; Monocarboxylic acid wherein, its chemical formula can be expressed as RCOOH, and R is the alkyl or aryl greater than 10 carbon in the formula, and this monocarboxylic acid comprises undecanoic acid, stearic acid, Palmiticacid or phenylformic acid.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB001190660A CN1142203C (en) | 2000-10-20 | 2000-10-20 | Semi-crystalline dendritic polyether amide oligomer capable of being radiation cured and its prepn |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB001190660A CN1142203C (en) | 2000-10-20 | 2000-10-20 | Semi-crystalline dendritic polyether amide oligomer capable of being radiation cured and its prepn |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1350021A true CN1350021A (en) | 2002-05-22 |
| CN1142203C CN1142203C (en) | 2004-03-17 |
Family
ID=4587460
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CNB001190660A Expired - Fee Related CN1142203C (en) | 2000-10-20 | 2000-10-20 | Semi-crystalline dendritic polyether amide oligomer capable of being radiation cured and its prepn |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN1142203C (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100391937C (en) * | 2005-05-25 | 2008-06-04 | 长兴化学工业股份有限公司 | Acrylic acid semicrystal super branched polycarbamate oligo polymer and its preparation method |
| CN109957083A (en) * | 2017-12-25 | 2019-07-02 | 江苏百赛飞生物科技有限公司 | A kind of manufacturing method of unsaturated polyol and photocurable polyurethane and they prepared therefrom |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP5899140B2 (en) * | 2013-03-14 | 2016-04-06 | 富士フイルム株式会社 | Polymerizable fluorine-containing compound, curable composition, film, separation wall, antireflection film, and display device |
-
2000
- 2000-10-20 CN CNB001190660A patent/CN1142203C/en not_active Expired - Fee Related
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100391937C (en) * | 2005-05-25 | 2008-06-04 | 长兴化学工业股份有限公司 | Acrylic acid semicrystal super branched polycarbamate oligo polymer and its preparation method |
| CN109957083A (en) * | 2017-12-25 | 2019-07-02 | 江苏百赛飞生物科技有限公司 | A kind of manufacturing method of unsaturated polyol and photocurable polyurethane and they prepared therefrom |
| CN109957083B (en) * | 2017-12-25 | 2021-06-29 | 江苏百赛飞生物科技有限公司 | Unsaturated polyol, photocurable polyurethane prepared from unsaturated polyol and preparation methods of unsaturated polyol and photocurable polyurethane |
Also Published As
| Publication number | Publication date |
|---|---|
| CN1142203C (en) | 2004-03-17 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| Honglu et al. | Wood liquefaction by ionic liquids | |
| CN1931834A (en) | Synthesis process of phenyl dimethylene diisocyanate | |
| CN1147522C (en) | Radiation-curable amino superbranching polyester and preparation process thereof | |
| CN107188802B (en) | Method for catalyzing alcohol to depolymerize 3-hydroxybutyrate by using double-acid ionic liquid | |
| JP5265116B2 (en) | Acrylic modified polybutadiene | |
| Zanela et al. | Chemical recycling of poly (ethylene terephthalate)(PET) by alkaline hydrolysis and catalyzed glycolysis | |
| CN1131662A (en) | Perfluoro unsaturated nitrile compound and process for producing the same | |
| CN1142203C (en) | Semi-crystalline dendritic polyether amide oligomer capable of being radiation cured and its prepn | |
| CN102548966B (en) | Method for synthesis of N-alkyl carbazole and derivatives thereof | |
| CN110387000A (en) | Benzophenone analog derivative photoinitiator and preparation method | |
| JP6025476B2 (en) | Process for producing ethylenically unsaturated group-containing isocyanate compound | |
| Alzuhairi et al. | Nano MgO catalyst for chemical depolymerization of polyethylene terephthalate (PET) | |
| CN101624408A (en) | Pendant naphthalene group-containing benzene ligand ferrocenium salt cationic photoinitiators and preparation method thereof | |
| CN1304359C (en) | Process for synthesizing propylene glycol methyl ether acetate | |
| CN110152648A (en) | Preparation method, tin catalyst and its application of tin catalyst | |
| JP4802343B2 (en) | Method for producing styrene derivative | |
| CN1665848A (en) | Polymerizing hydrogels including modifying compounds to comprise low amount of residual monomers and by-products and to optimize material properties | |
| CN110317346B (en) | Dendritic fluorescein sodium-iodonium salt visible light initiator and preparation method and application thereof | |
| CN1660837A (en) | Light mitiator of thioxanthone-2-carboxylic ester | |
| JP2008285457A (en) | Method for producing glycerol carbonate | |
| CN1869007A (en) | Acrylic acid semicrystal super branched polycarbamate oligo polymer and its preparation method | |
| Cao et al. | Efficient synthesis of dimethyl hexane-1, 6-dicarbamate via methoxycarbonylation of 1, 6-hexanediamine with methyl carbamate over acid-base enhanced CeO2 | |
| TWI797953B (en) | A non-phosgene process for preparing polyurethanes and their intermediates | |
| CN1228316C (en) | Chemical synthesis of p-methoxyphenyl isocyanate | |
| Kirino et al. | Aminimide derived from benzoylformic acid ester as photolatent base/radical initiator |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C06 | Publication | ||
| PB01 | Publication | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant | ||
| C19 | Lapse of patent right due to non-payment of the annual fee | ||
| CF01 | Termination of patent right due to non-payment of annual fee |