CN103849348B - A kind of composition of polyester hot-melt adhesive and preparation method thereof - Google Patents
A kind of composition of polyester hot-melt adhesive and preparation method thereof Download PDFInfo
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- CN103849348B CN103849348B CN201210516646.6A CN201210516646A CN103849348B CN 103849348 B CN103849348 B CN 103849348B CN 201210516646 A CN201210516646 A CN 201210516646A CN 103849348 B CN103849348 B CN 103849348B
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Abstract
The present invention relates to a kind of composition of polyester hot-melt adhesive and preparation method thereof.It comprises: a) polyester diol, and it is dicarboxylic acid component and C
2-6the polycondensation product of diol component, described dicarboxylic acid component comprises terephthalic acid and non-essential m-phthalic acid and C
4-12aliphatic dicarboxylic acid's unit, its weight-average molecular weight is 10000 ~ 100000, and b) C
16-20lipid acid strontium.Composition of polyester hot-melt adhesive of the present invention has good mobility and melt stability.
Description
Technical field
The present invention relates to a kind of composition of polyester hot-melt adhesive and preparation method thereof, particularly relate to composition of polyester hot-melt adhesive of high fluidity and melt stability and preparation method thereof.
Background technology
Polyester hot-melt adhesive is a kind of environmental protection, free of contamination green tackiness agent, is obtained after esterification (or transesterify), polycondensation by one or more diprotic acid (or ester) and dibasic alcohol.The coating method of polyester hot-melt adhesive is generally fusion coating, and therefore under certain temperature, the mobility of glue has a great impact the quality of coating and efficiency.The good fluidity of glue, then coating or forming process temperature low, less energy consumption, surface covered and quality might as well; The poor fluidity of glue, perviousness during coating, spreadability are also poor, not only increase the consumption of glue, also have impact on adhesiveproperties.Owing to being high-temperature fusion coating, also require that polyester hot-melt adhesive has good melt stability.
Prior art is add flow ability modifying agent to carry out screw rod blended improving the major measure in polyester mobility.For production of polyester enterprise, screw rod is blended adds operation and cost, have impact on production efficiency.
Therefore, in this area in the urgent need to the polyester hot-melt adhesive of a kind of good fluidity and melt stability.
Summary of the invention
Main order of the present invention is to provide a kind of good fluidity and composition of polyester hot-melt adhesive of melt stability and preparation method thereof.
The composition of polyester hot-melt adhesive of a kind of high workability of the present invention comprises:
A) polyester diol, it is dicarboxylic acid component and C
2-6the polycondensation product of diol component, described dicarboxylic acid component comprises terephthalic acid and non-essential C
4-12aliphatic dicarboxylic acid and m-phthalic acid, its weight-average molecular weight is 10000 ~ 100000, and
B) C
16-20lipid acid strontium.
The present invention also provides a kind of preparation method of composition of polyester hot-melt adhesive of high workability, and it comprises the steps:
1) make to comprise terephthalic acid and non-essential C
4-12the dicarboxylic acid component of aliphatic dicarboxylic acid and m-phthalic acid and C
2-6diol component carries out polycondensation, and
2) in polycondensation product, C is added
16-20lipid acid strontium.
The present invention is by using C
16-20lipid acid strontium carries out modification to polyester diol, and make to synthesize the polyester hot-melt adhesive obtained and have high mobility, have good melt stability and bonding strength simultaneously, the low cost of manufacture of this high flow polyester hot-melt adhesive composition, is easily coated with.
Embodiment
In one preferred embodiment, polyester diol of the present invention contains 30 ~ 100 % by mole of terephthalic acids, 0 ~ 70 % by mole of m-phthalic acid and 0 ~ 70 % by mole of C
4-12aliphatic dicarboxylic acid, preferably containing 30 ~ 90 % by mole of terephthalic acid units, 5 ~ 45 % by mole of isophthalic acid units and 5 ~ 45 % by mole of C
6-10aliphatic dicarboxylic acid's unit, with the total mole number of dicarboxylic acid component in described polyester diol for benchmark.
In a preferred embodiment, described polyester diol contains 50 ~ 80 % by mole of terephthalic acid units, 10 ~ 30 % by mole of isophthalic acid units and 10 ~ 30 % by mole of C
6-10aliphatic dicarboxylic acid's unit, with the total mole number of dicarboxylic acid component in described polyester diol for benchmark.
Above-mentioned terephthalic acid, m-phthalic acid and C
4-12aliphatic dicarboxylic acid's unit can by terephthalic acid, m-phthalic acid and C
4-12aliphatic dicarboxylic acid or their C
1-4alkyl ester produces.
C
4-12the example of aliphatic dicarboxylic acid comprises succinic acid, hexanodioic acid, pimelic acid, suberic acid, nonane diacid, sebacic acid, undecane dicarboxylic acid and dodecanedicarboxylic acid or their mixture, preferably succinic acid, hexanodioic acid, suberic acid, sebacic acid or their mixture, is more preferably hexanodioic acid, sebacic acid or their mixture.
Above-mentioned di-carboxylic acid C
1-4the example of alkyl ester comprises dimethyl terephthalate (DMT), diethyl terephthalate, terephthalic acid dipropyl, dibutyl terephthalate, dimethyl isophthalate, dimethyl isophthalate, m-phthalic acid dipropyl, m-phthalic acid dibutylester, dimethyl succinate, Methyl glutarate, dimethyl adipate, Polycizer W 260, NSC 52563, pimelic acid dibutylester, suberic acid dimethyl ester, suberic acid dibutylester, dimethyl azelate, dibutyl azelate, dimethyl sebacate, Uniflex DBS etc.Preferably dimethyl terephthalate (DMT), dimethyl isophthalate, dimethyl adipate, dimethyl sebacate.
Above-mentioned diol component comprises at least one dibasic alcohol be selected from ethylene glycol, propylene glycol, butyleneglycol, pentanediol, hexylene glycol.Above-mentioned dibasic alcohol can be used alone, also can two or more is used in combination.
In one preferred embodiment, described C
16-20lipid acid strontium accounts for 0.1 ~ 5 % by weight of polyester diol total mole number, preferably accounts for 0.3 ~ 2 % by weight.
In a preferred embodiment, described C
16-20lipid acid strontium is C
16-20saturated fatty acid strontium, is more preferably strontium stearate.
In the polycondensation of dibasic acid component and diol component, polycondensation together with can making under the effect at catalyzer of above-mentioned dibasic acid component and diol component, obtain polyester diol of the present invention, but in order to improve speed of reaction, generally first make the di-carboxylic acid C that reactive behavior is lower
1-4alkyl ester and dibasic alcohol carry out transesterification reaction, such as, first make terephthaldehyde's acid alkyl ester and dibasic alcohol carry out transesterification reaction.The temperature range of transesterification reaction is generally 100 ~ 250 ° of C, is preferably 140 ~ 240 ° of C.This transesterification reaction can be carried out at ambient pressure, also can reduce pressure down and carry out.When water outlet reaches theoretical value 95%, esterification terminates.Continue to be warming up to 240 ~ 260 ° of C, under the condition vacuumizing decompression step by step, carry out copolycondensation, obtained polyester hot-melt adhesive.In reactor, be filled with nitrogen, remove vacuum to atmospheric pressure state.Under agitation to 1) polycondensation product in add C
16-20lipid acid strontium, continues stirring reaction 10 ~ 30 minutes, namely obtains composition of polyester hot-melt adhesive of the present invention.
In one preferred embodiment, the mol ratio of above-mentioned di-carboxylic acid or its alkane ester component and diol component is preferably 1:(1.1 ~ 2), be preferably 1:(1.2 ~ 1.8), most preferably be 1:(1.2 ~ 1.6) left and right.
Catalyzer conventional in this area can be used, as metatitanic acid alkane ester, as metatitanic acid four methyl esters, tetraethyl titanate, metatitanic acid orthocarbonate, tetrabutyl titanate in above-mentioned transesterification reaction.
In the present invention, the consumption of catalyzer is about 0.01 ~ 0.15 % by weight of starting monomer gross weight, is preferably 0.01 ~ 0.1 % by weight.
When the alcohol distillated from transesterification reaction system reaches theoretical amount, when the water distillated from esterification system reaches theoretical amount, temperature is continued to be increased to 240 ~ 260 ° of C gradually, apply the vacuum being less than about 133Pa, carry out polycondensation, to remove remaining water and monomer from reaction system.For preventing reactant from discharging system, vacuumizing and answering proceed step by step, proceeding to high vacuum from rough vacuum gradually.The overbottom pressure of final system is lower than 133Pa.
Catalyzer and stablizer can be added in polycondensation reaction system.
Polycondensation catalyst still can with above-mentioned metatitanic acid alkane ester, and add-on is about 0.01 ~ 0.15 % by weight of formation polyester hot-melt adhesive gross weight, is preferably 0.01 ~ 0.1 % by weight.
After polycondensation completes, stop heating, preferably under the inert atmosphere of nitrogen and so on, the temperature of reaction mixture is cooled to 100 ° of below C.Then in this reaction mixture, C is added
16-20lipid acid strontium and other optional additive, as stablizer and nucleator, oxidation inhibitor, tinting material, weighting agent etc.After stirring, cooling, pelletizing, i.e. obtained composition of polyester hot-melt adhesive product of the present invention.
The example of stablizer comprises phosphoric acid ester and phosphorous acid ester.
The example of phosphoric acid ester comprises trimethyl phosphite 99, triethyl phosphate, tributyl phosphate or their mixture.
The example of phosphorous acid ester comprises triphenyl phosphite, triethyl-phosphite, tributyl phosphate or their mixture.
The consumption of stablizer is generally about 0.01 ~ 0.1 % by weight of starting monomer gross weight, is preferably 0.02 ~ 0.08 % by weight.
The example of nucleator comprises the one in superfine silicon dioxide, talcum powder and carboxylic acid sodium salt, preferably adopts carboxylic acid sodium salt.
The consumption of nucleator is generally the 0.01-1.5% of reaction after product gross weight, is preferably 0.1-1%.
Above-mentioned metatitanic acid alkane ester catalyst also can catalytic esterification and polycondensation.
After polycondensation terminates, gained reaction product is cooled, measure (weight average) molecular weight by gel chromatography (GPC) method.The weight-average molecular weight of polyester diol of the present invention is generally 10000 ~ 100000, is preferably 20000 ~ 50000.
Above-mentioned polyester diol and synthetic method thereof such as can see CN1990810A.
The preparation method of composition of polyester hot-melt adhesive of the present invention can be directly blended in reactor, has the advantage that production efficiency is high, production cost is low.
Composition of polyester hot-melt adhesive obtained as stated above has low melt viscosity and low specific viscosity rate of descent, and the composition of polyester hot-melt adhesive of this high workability can replace Solvent Adhesive and directly apply to coating process.
Embodiment
Following embodiment is used for further illustrating the present invention, but is to be understood that these embodiments can not be used for limiting the scope of the invention.Protection scope of the present invention is limited by appending claims.
Polyester hot-melt adhesive test performance in accordance with the following methods obtained in each embodiment and comparative example:
Mobility: evaluated by the melt viscosity testing polyester, under uniform temp, melt viscosity is lower, then mobility is better.
Melting heat stability: polyester hot-melt adhesive is placed 6 hours in 230 DEG C of DEG C of baking ovens, tests the value of specific viscosity after 6 hours, and calculate the rate of descent of specific viscosity before and after placing, rate of descent is lower, and its melt stability is better.
The testing method of melt viscosity: correct amount 11g polyester hot-melt adhesive sample, dry moisture in an oven, adopt the test of Brookfield DV-E type rotational viscosimeter, probe temperature is 230 DEG C, rotor S27, record rotor runs up the melt viscosity value of dial plate display after 30min, and rotating speed adjusts according to practical situation.
Specific viscosity is tested: by standard GB/T/T1632-93, and adopt Ubbelohde viscometer method to carry out specific viscosity test, for characterizing the size of its molecular weight, solvent for use is phenol tetrachloroethane (weight ratio is 1:1).
Fusing point: the DSC-823c test adopting Mettler, through twice heating scan, heating rate is 20 DEG C/min, and the melting peak temperature that second time heats up is fusing point.
Embodiment 1
1 is added in a 1L reactor leaning on condenser with thermometer, mechanical stirrer, fractionation, 4-butyleneglycol 234 grams, under agitation adds terephthalic acid 232.4 grams immediately, m-phthalic acid 33.2 grams, hexanodioic acid 58.4 grams, and the positive ethyl ester of phthalandione 0.23 gram.Heat temperature raising, when being warmed up to about 170 DEG C, starts to distillate water droplet, heats up in a steamer temperature 90 ~ 100 DEG C, and continue heating direct to temperature in the kettle and reach about 220 DEG C, when water quantity of distillate reaches theoretical amount, esterification completes, and obtains low-molecular-weight oligopolymer.Continue temperature to rise to about 240 ~ 250 DEG C, and improve the vacuum tightness of system, until the vacuum tightness of system is less than 133Pa.When polycondensation power reaches preset value, be filled with nitrogen and remove vacuum to normal pressure, add strontium stearate (purchased from upper hamming too chemical company) 3.4 grams, continue stirring 20 minutes, while hot molten materials is poured in cold water, obtain white adhesive tape, be cut into micelle, namely obtain composition of polyester hot-melt adhesive of the present invention.
At 100 DEG C after dry 6 hours, the fusing point recorded 176 DEG C, specific viscosity is 0.39, and melt viscosity is 20800mPa.S/230 DEG C.After by dried polyester hot-melt adhesive particle, in 230 DEG C of baking ovens, melting places 6 hours, testing its specific viscosity is 0.36.
Embodiment 2,3 and 4
Above three embodiments are undertaken by the step identical with embodiment 1 and condition, difference be raw materials used and proportioning as shown in table 1 below.The analytical results of products therefrom is also listed in table 1.
Comparative example 1
1 is added in a 1L reactor leaning on condenser with thermometer, mechanical stirrer, fractionation, 4-butyleneglycol 234 grams, under agitation adds terephthalic acid 232.4 grams immediately, m-phthalic acid 33.2 grams, hexanodioic acid 58.4 grams, and the positive ethyl ester of phthalandione 0.23 gram.Heat temperature raising, when being warmed up to about 170 DEG C, starts to distillate water droplet, heats up in a steamer temperature 90 ~ 100 DEG C, and continue heating direct to temperature in the kettle and reach about 220 DEG C, when water quantity of distillate reaches theoretical amount, esterification completes, and obtains low-molecular-weight oligopolymer.Continue temperature to rise to about 240 ~ 250 DEG C, and improve the vacuum tightness of system, until the vacuum tightness of system is less than 133Pa.When polycondensation power reaches preset value, be filled with nitrogen and remove vacuum to normal pressure, while hot molten materials is poured in cold water, obtain white adhesive tape, be cut into micelle.
At 100 DEG C after dry 6 hours, the fusing point recorded 176 DEG C, specific viscosity is 0.39, and melt viscosity is 31300mPa.S/230 DEG C.After by dried polyester hot-melt adhesive particle, in 230 DEG C of baking ovens, melting places 6 hours, testing its specific viscosity is 0.34.
Comparative example 2
Comparative example 2 is undertaken by the step and method of comparative example 1, and difference is raw material and proportioning thereof, as shown in table 1 below, and the analytical results of products therefrom is also listed in table 1.
Comparative example 3 and 4
Above two comparative examples are undertaken by the step and method of embodiment 1, and difference is raw material and proportioning, as shown in table 1, and the analytical results of products therefrom is also listed in table 1.
The formula of each embodiment of table 1 and comparative example and analytical results
Note a: the data of comparative example 1,2,3,4 and effect correspond respectively to embodiment 1,2,3,4.
In above table 1, embodiment 1,2,3,4 is the example adopting strontium stearate modification, and comparative example 1,2 is the example not adopting properties-correcting agent, and comparative example 3,4 is respectively the example adopting properties-correcting agent calcium stearate and Zinic stearas.
By table in data can be clear that, add in embodiment 1,2,3,4 gained polyester hot-melt adhesive strontium stearate blended after, mixture melt viscosity obviously declines, and flowing property improves greatly; Comparative example 1 and 2 does not add strontium stearate, and then melt viscosity is apparently higher than embodiment 1 and 2, and comparative example 3 and 4 adopts calcium stearate and Zinic stearas modification then to reduce melt viscosity effect not as embodiment 3,4 obvious respectively.
As can also be seen from Table 1, embodiment 1,2,3,4 gained polyester hot-melt adhesive, after 230 DEG C of meltings place 6 hours, the rate of descent of its specific viscosity is less than the specific viscosity rate of descent of comparative example 1,2,3,4 gained polyester hot-melt adhesive respectively.This illustrates, embodiment 1,2,3,4 gained polyester hot-melt adhesive has better melting heat stability.Table 1 it can also be seen that, the polyester hot-melt adhesive (embodiment 1,3) that fusing point is high has better melting heat stability than low-melting polyester hot-melt adhesive (embodiment 2,4).
That is, polyester hot-melt adhesive of the present invention in the molten state degradation speed is slower, and this is obviously more favourable to melt coating, does not worry that hot melt adhesive is degraded too fast and affects coating quality and cohesive strength in molten groove.
Surprisingly, by adding strontium stearate and the blended composition of polyester hot-melt adhesive of the present invention obtained of polyester hot-melt adhesive in reactor, not only there is better mobility, and there is better thermostability in the molten state.And add the salt such as calcium stearate of the same type, Zinic stearas, then do not reach same effect.
In addition, composition of polyester hot-melt adhesive of the present invention directly in reactor high-temperature blending obtain, need not increase blending equipment, blend composition consistency is good, and without any peculiar smell, therefore production efficiency is high, and production cost is low.
Claims (9)
1. a composition of polyester hot-melt adhesive for high workability, it comprises:
A) polyester diol, it is dicarboxylic acid component and C
2-6the polycondensation product of diol component, described dicarboxylic acid component comprises terephthalic acid and non-essential C
4-12aliphatic dicarboxylic acid and m-phthalic acid, its weight-average molecular weight is 10000 ~ 100000, and
B) C
16-20lipid acid strontium, described C
16-20lipid acid strontium accounts for 0.3 ~ 2 % by weight of polyester diol gross weight.
2. composition of polyester hot-melt adhesive as claimed in claim 1, it is characterized in that, in the total mole number of dicarboxylic acid component in described polyester diol, the content of terephthalic acid is 30 ~ 100 % by mole, and the content of m-phthalic acid is 0 ~ 70 % by mole, C
4-12the content of aliphatic dicarboxylic acid is 0 ~ 70 % by mole.
3. composition of polyester hot-melt adhesive as claimed in claim 2, it is characterized in that, in the total mole number of dicarboxylic acid component in described polyester diol, the content of terephthalic acid is 30 ~ 90 % by mole, and the content of m-phthalic acid is 5 ~ 45 % by mole, and C
6-10the content of aliphatic dicarboxylic acid is 5 ~ 45 % by mole.
4. the composition of polyester hot-melt adhesive according to any one of claim 1 ~ 2, is characterized in that, described C
4-12aliphatic dicarboxylic acid selects oneself diacid, suberic acid, sebacic acid and their mixture.
5. composition of polyester hot-melt adhesive as claimed in claim 4, is characterized in that, described C
4-12aliphatic dicarboxylic acid selects oneself diacid, sebacic acid and their mixture.
6. composition of polyester hot-melt adhesive as claimed in claim 1, is characterized in that described C
2-6dibasic alcohol comprises two or more dibasic alcohol be selected from ethylene glycol, propylene glycol, butyleneglycol, hexylene glycol.
7. composition of polyester hot-melt adhesive as claimed in claim 1, is characterized in that, described C
16-20lipid acid strontium is C
16-20saturated fatty acid strontium.
8. composition of polyester hot-melt adhesive as claimed in claim 1, is characterized in that, described C
16-20lipid acid strontium is strontium stearate.
9. the preparation method of the composition of polyester hot-melt adhesive according to any one of claim 1-8, it comprises the steps:
1) make to comprise terephthalic acid and non-essential C
4-12the dicarboxylic acid component of aliphatic dicarboxylic acid and m-phthalic acid and C
2-6diol component carries out polycondensation, and
2) in polycondensation product, C is added
16-20lipid acid strontium.
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| CN104479116B (en) * | 2014-12-04 | 2016-12-07 | 金发科技股份有限公司 | A kind of preparation method of poly terephthalic acid M-phthalic acid adipic acid/butanediol copolyester |
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| US7300998B2 (en) * | 2002-02-14 | 2007-11-27 | Mitsui Chemicals, Inc. | Polyester resin and catalyst for polyester production, process for producing polyester resin with the catalyst, polyester resin obtained with the catalyst, and hollow molded container comprising the polyester resins |
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Effective date of registration: 20170607 Address after: 200031 Shanghai Xuhui District City Baoqing Road No. 20 Co-patentee after: Liri Chemical New Materials Co., Ltd. Shanghai Patentee after: Shanghai Light Industry Research Institute Co., Ltd. Address before: 200031 Shanghai Xuhui District City Baoqing Road No. 20 Patentee before: Shanghai Light Industry Research Institute Co., Ltd. |