CN1308410C - Composition of polyester hot-melt adhesive in low melting viscosity - Google Patents
Composition of polyester hot-melt adhesive in low melting viscosity Download PDFInfo
- Publication number
- CN1308410C CN1308410C CNB2005101103383A CN200510110338A CN1308410C CN 1308410 C CN1308410 C CN 1308410C CN B2005101103383 A CNB2005101103383 A CN B2005101103383A CN 200510110338 A CN200510110338 A CN 200510110338A CN 1308410 C CN1308410 C CN 1308410C
- Authority
- CN
- China
- Prior art keywords
- polyester
- melt adhesive
- acid
- composition
- polyester hot
- 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.)
- Expired - Fee Related
Links
Landscapes
- Adhesives Or Adhesive Processes (AREA)
- Polyesters Or Polycarbonates (AREA)
Abstract
The present invention provides a composition of polyester hot melt adhesive with low melting viscosity. The composition of polyester hot melt adhesive contains 90 to 94 wt% of polyesterglycol and 6 to 10 wt% of superbranched polyester measured according to the total weight of the composition of polyester hot melt adhesive, wherein the polyesterglycol is condensation polymerization reaction products of a dicarboxylic acid component and C2 to C6 dibasic alcohol components. The dicarboxylic acid component contains terephthalic acid, isophthalic acid and inessential C6 to C12 aliphatic dicarboxylic acid units, and the weight average molecular weight of the dicarboxylic acid component is from 27000 to 37500. The superbranched polyester is formed by the copolymeration of 3, 5-dihydroxytoluene and 3, 5-dihydroxy-benzoic acid whose molar ratio is 1:6 to 10, and the weight average molecular weight of the superbranched polyester is from 2000 to 4500. Not only can the composition of polyester hot melt adhesive of the present invention be uniformly and rapidly coated, but also the use amount of polyester hot melt adhesive can be reduced.
Description
Technical field
The present invention relates to the low composition of polyester hot-melt adhesive of a kind of composition of polyester hot-melt adhesive, particularly melt viscosity.
Background technology
Present known polyester hot-melt adhesive all adopts aromatic acid (or dibasic acid dimethyl ester) such as terephthalic acid and long carbochain aliphatic dibasic acid (or dibasic acid dimethyl ester), dibasic alcohol to obtain after esterification (or transesterify), polycondensation.As U.S. Pat 6,255, a kind of copolyester with low melting point and polyether ester hot melt adhesive have been disclosed in 443.
Yet, because the apparent viscosity of this polyester hot-melt adhesive product is generally all bigger, is difficult to carry out Rapid and uniform coating, thereby has influenced surface covered, increased coating amount.
Summary of the invention
The purpose of this invention is to provide the low composition of polyester hot-melt adhesive of a kind of melt viscosity, thereby can carry out Rapid and uniform coating, not only can accelerate surface covered, and can reduce the consumption of polyester hot-melt adhesive.
Composition of polyester hot-melt adhesive of the present invention contains in its gross weight:
A) 90～94 weight % polyester diol, it is di-carboxylic acid component and C
2-6The polycondensation product of diol component, described di-carboxylic acid component comprise terephthalic acid and m-phthalic acid and non-essential C
6-12Aliphatic dicarboxylic acid unit, molecular weight are 27000-37500.
B) 6～10 weight % hyper-branched polyesters.
The fusing point of polyester hot-melt adhesive of the present invention is generally 60～120 ℃.This polyester hot-melt adhesive has fast crystalline characteristic, adopts the DSC test result to have tangible melting peak, and cold crystallization peak temperature is not obvious; This polyester hot-melt adhesive has low melt viscosity, and melt viscosity is less than 40Pa.s in the time of 160 ℃.
Embodiment
Synthesizing of polyester diol:
Used polyester diol is di-carboxylic acid component and C among the present invention
2-6The polycondensation product of diol component.
Above-mentioned di-carboxylic acid component comprises terephthalic acid and m-phthalic acid and non-essential C
6-12The aliphatic dicarboxylic acid unit.
Above-mentioned terephthalic acid, m-phthalic acid and C
6-12The aliphatic dicarboxylic acid unit can be by terephthalic acid, m-phthalic acid and C
6-12Aliphatic dicarboxylic acid or their C
1-4Alkyl ester produces.
C
6-12Aliphatic dicarboxylic acid's example comprises hexanodioic acid, pimelic acid, suberic acid, nonane diacid, sebacic acid, 11 methylene radical dicarboxylic acid and ten dimethylene dicarboxylic acid or their mixture, preferably hexanodioic acid, suberic acid, sebacic acid or their mixture are more preferably sebacic acid.
Above-mentioned di-carboxylic acid C
1-4The example of alkyl ester comprises dimethyl terephthalate (DMT), diethyl terephthalate, the terephthalic acid dipropyl, dibutyl terephthalate, dimethyl isophthalate, dimethyl isophthalate, the m-phthalic acid dipropyl, the m-phthalic acid dibutylester, dimethyl adipate, Polycizer W 260, NSC 52563, the pimelic acid dibutylester, the suberic acid dimethyl ester, the suberic acid dibutylester, dimethyl azelate, dibutyl azelate, dimethyl sebacate, Uniflex DBS, ten dimethylene dimethyl dicarboxylates, ten dimethylene dicarboxylic acid dibutylesters or the like.Preferably dimethyl terephthalate (DMT), dimethyl isophthalate, dimethyl adipate, suberic acid dimethyl ester, dimethyl sebacate.
For fusing point that reduces polyester diol and the crystallization velocity that improves polyester diol, total mole number in di-carboxylic acid component in the used polyester diol of the present invention, the content of terephthalic acid units is 50～80 moles of %, be preferably 50～75 moles of %, the unitary content of m-phthalic acid is 10～40 moles of %, be preferably 10～35 moles of %, C
6-12The unitary content of aliphatic dicarboxylic acid is 0～20 mole of %, is preferably 10～20 moles of %.
Above-mentioned diol component comprises at least a dibasic alcohol that is selected from ethylene glycol, propylene glycol, butyleneglycol, pentanediol, hexylene glycol, glycol ether and the Triethylene glycol.Above-mentioned dibasic alcohol can use separately, also can two kinds or multiple mixing use.Preferred two kinds and the two or more mixing dibasic alcohol that adopts in ethylene glycol, butyleneglycol, the hexylene glycol.In the total mole number of dibasic alcohol in the used polyester diol of the present invention, glycol content is 0-50 mole %, is preferably 10～30 moles of %, the content of butyleneglycol is 0-70 mole %, be preferably 10～50 moles of %, the content of hexylene glycol is 30-70 mole %, is preferably 50～70 moles of %.
The mol ratio of above-mentioned di-carboxylic acid or its alkane ester component and diol component is preferably 1: (1.5～2.5) are preferably 1: (1.7～2.2) most preferably are 1: 2.0.
In the polycondensation of dibasic acid component and diol component, next reacts in the effect of catalyzer can to make above-mentioned dibasic acid component and diol component, obtain low-melting point polyester dibasic alcohol of the present invention, but, generally make the lower di-carboxylic acid C of reactive behavior earlier in order to improve speed of reaction
1-4Alkyl ester and dibasic alcohol carry out transesterification reaction, for example make terephthaldehyde's acid alkyl ester and dibasic alcohol carry out transesterification reaction earlier.The temperature range of transesterification reaction is generally 100～250 ℃, is preferably 130～210 ℃.This transesterification reaction can be carried out under normal pressure, also can reduce pressure down and carry out.
Can use catalyzer conventional in this area in the above-mentioned transesterification reaction, as metatitanic acid alkane ester, as metatitanic acid tetramethyl ester, tetraethyl titanate, metatitanic acid orthocarbonate, tetrabutyl titanate.
Catalyst consumption is about 0.020～0.085 weight % of starting monomer gross weight among the present invention, is preferably 0.025～0.075 weight %.
When distilled alcohol reaches theoretical amount from the transesterification reaction system, stop heating, the temperature of reaction mixture is cooled to below 100 ℃.In this reaction mixture, add remaining di-carboxylic acid or ester then, reheat, carry out esterification.Esterification temperature is generally 140～210 ℃.When distillating the water yield when reaching theoretical amount, continue temperature is increased to 240～260 ℃ gradually, apply the vacuum that is less than about 133Pa, carry out polycondensation, from reaction system, to remove remaining water and monomer.
Can add stablizer and nucleator in esterification and the polycondensation reaction system.The example of stablizer comprises phosphoric acid ester and phosphorous acid ester, and the example of nucleator comprises and a kind of in superfine silicon dioxide, talcum powder and the carboxylic acid sodium salt preferably adopts carboxylic acid sodium salt.
The example of phosphoric acid ester comprises trimethyl phosphite 99, triethyl phosphate, tributyl phosphate.
The example of phosphorous acid ester comprises triphenyl phosphite, triethyl-phosphite and tributyl phosphate.
The consumption of stablizer generally is about 0.020～0.085 weight % of starting monomer gross weight, is preferably 0.025～0.075 weight %.
The consumption of nucleator is generally the 0.01-1.5% of reaction after product gross weight, is preferably 0.1-1%.
But above-mentioned also catalytic esterification and polycondensation of metatitanic acid alkane ester catalyst.
After polycondensation finishes,, measure (weight average) molecular weight with gel chromatography (GPC) method with the cooling of gained reaction product.The weight-average molecular weight of polyester diol of the present invention is generally 27000～37500, is preferably 34000～37500.
Adopt the melt viscosity of Brookfield DV-E type rotational viscosimeter specimen.When temperature was controlled at 160 ℃, melt viscosity was generally greater than 80Pa.s, usually greater than 100Pa.s.
Above-mentioned polyester diol and synthetic method thereof for example can be referring to United States Patent (USP) 6,255,443.
Synthesizing of hyper-branched polyester:
The used hyper-branched polyester of the present invention is by 3,5-dihydroxyl C
1-2Alkylbenzene and 3, the copolymerization of 5-resorcylic acid forms, preferably by 3,5-orcin and 3, the copolymerization of 5-resorcylic acid forms.3,5-dihydroxyl C
1-2Alkylbenzene and 3, the mol ratio of 5-resorcylic acid is 1: 6～10, be preferably 1: 7～10.The weight-average molecular weight that records with the gpc analysis method is 2000～4500, is preferably 2000～3000.
The synthetic hyper-branched polyester adopts infrared analysis, sees that this polyester has two key bands, at 1750-1714cm and 1298.3-1136.1cm very strong absorption peak is arranged, and is respectively carbonylic stretching vibration absorption peak and C-O stretching vibration absorption peak.
The synthetic hyper-branched polyester adopts dsc analysis, 20 ℃/min of heat-up rate, and recording fusing point is 70-90 ℃, is preferably 75-90 ℃.
The structure of synthetic hyper-branched polyester and synthetic method thereof can be referring to Cao Shengguang, Weng Jiabao " the synthetic and sign of hyper-branched polyester ", Fujian Normal University's journal (natural science edition), 2001,17 (2): 62-65.
Composition of polyester hot-melt adhesive
The polyester diol heating and melting that 90～94 weight parts are above-mentioned, add the above-mentioned hyper-branched polyester of 6～10 weight parts then, fully mix, while hot molten materials is poured in the cold water, obtain transparent or the water white adhesive tape, and be cut into micelle, obtain the composition of polyester hot-melt adhesive of low melting viscosity of the present invention.
Adopt the melt viscosity of Brookfield DV-E type rotational viscosimeter specimen.When temperature was controlled at 160 ℃, melt viscosity generally was lower than 50Pa.s, preferably was lower than 40Pa.s.
Embodiment
Embodiment 1
In 1000 milliliters of stainless steel cauldrons that thermometer, mechanical stirrer, dimension Ge Shi fractional column and condenser be housed, add dimethyl terephthalate (DMT) 194 grams, 1,6-hexylene glycol 236 grams, ethylene glycol 124 grams and tetraethyl titanate 0.23 restrain.Heat temperature raising when temperature in the kettle reaches 100 ℃, starts stirring immediately.When being warmed up to 145 ℃ of left and right sides, begin to distillate the methyl alcohol drop, heat up in a steamer warm 60-80 ℃, continuing to heat up reaches about 200 ℃ until temperature in the kettle, and when treating the methyl alcohol quantity of distillate greater than theoretical amount 97%, transesterify is finished, and stops heating, cooling.
When temperature in the aforesaid reaction vessel is reduced to below 100 ℃, promptly add m-phthalic acid 100 grams, sebacic acid 81 grams, and adding triphenyl phosphite 0.2 gram and 4 gram medical talc powders, stir then and heat up, when in the still about degree temperature rise to 160 ℃, there is water to distillate, heat up in a steamer temperature generally at 90-105 ℃, continue to be warming up to about 210 ℃, the water quantity of distillate was greater than 98% o'clock of theoretical value, continue progressively temperature to be risen to about 250 ℃, carry out decompression vacuum pumping with vacuum pump, the vacuum tightness that keeps reaction system is less than 133Pa, and the continuation reaction was promptly finished polycondensation in about 2 hours under 250～255 ℃.Remove vacuum, while hot molten materials is poured in the cold water, obtain transparent or the water white adhesive tape, and be cut into micelle.
After under 50 ℃ dry 24 hours, 75 ℃ of the fusing points that records, 100 ℃ of softening temperatures, melt viscosity 120pa.s (160 ℃), viscosity ratio increment are 0.36, weight-average molecular weight is 28600.
Embodiment 2-10
Undertaken by step and the condition identical with embodiment 1, different is raw materials used and proportioning is as shown in table 1 below.The analytical results of products therefrom is also listed in the table 1.
Embodiment 11
With 5 kilograms of (32 moles) 3,5-resorcylic acid and 0.57 kilogram of (4 mole) 3, the 5-orcin adds in 100 liters of reactors, adding 4 grams, 98% vitriol oil is that catalyzer and 40 liters of hexanaphthenes are solvent, slowly be heated to 90 ℃ while stirring, cooling also distills out hexanaphthene and azeotrope water thereof, generates the xanchromatic solid until reacting completely.Add tetrahydrofuran (THF) and water washing, filter, dry the removing of vacuum constant temperature desolvated, and obtains yellow crystallite.
The weight-average molecular weight that records with the gpc analysis method is for being 2000～3000.
Embodiment 12
Take by weighing the low-melting point polyester dibasic alcohol that makes among the dried embodiment 1～10 of 184 grams respectively, heating and melting, add hyper-branched polyester 16 grams that make among the embodiment 11, fully mix, while hot molten materials is poured in the cold water, obtained transparent or the water white adhesive tape, and be cut into micelle, after under 50 ℃ dry 24 hours, adopt the melt viscosity of Brookfield DV-E type rotational viscosimeter specimen.
Take by weighing the polyester hot-melt adhesive sample of 11.0 grams, selecting model during test is the rotor of S27, and temperature is controlled at 160 ℃, and the continuous rotation rotating speed of regulating, and makes its test value be positioned at the linearity range of 10-90%, and observed value is write down in stable back.The results are shown in Table 1.
Table 1
| 1 | 2 | 3 | 4 | 5 | 6 | 7 | 8 | 9 | 10 | |
| Dimethyl terephthalate (DMT) (% by mole) M-phthalic acid (% by mole) decanedioic acid (% by mole) ethylene glycol (% by mole) butanediol (% by mole) hexylene glycol (% by mole) specific viscosity fusing point (℃) weight average molecular weight melt viscosity (Pa. s)/160 ℃ contains the melt viscosity (Pa. s) of 8% (wt%) hyper-branched polyester/160 ℃ | 50 30 20 50 50 0.36 75 28600 120 35 | 60 20 20 50 50 0.37 80 31900 150 40 | 70 10 20 50 50 0.38 95 33900 150 42 | 60 20 20 50 50 0.34 80 27000 90 20 | 65 35 50 50 0.40 89 35500 180 28 | 68 17 15 50 50 0.38 87 33200 160 26 | 70 10 20 50 50 0.39 88 34600 80 25 | 72 18 10 70 30 0.41 112 36500 190 46 | 80 20 33 67 0.42 90 37500 200 50 | 70 30 30 70 0.36 86 30000 80 27 |
Mole % in the table counts in the total mole number of di-carboxylic acid component and the total mole number of 100mol% dibasic alcohol.
Can be clear that by the data in the table, after adding a small amount of hyper-branched polyester in the polyester diol that in embodiment 1～10, makes, the melt viscosity of melted blend greatly reduces, thus the coating amount that helps improving the surface covered of polyester hot-melt adhesive and reduce polyester hot-melt adhesive.
Claims (9)
1. the composition of polyester hot-melt adhesive of low melting viscosity, in the gross weight of this composition of polyester hot-melt adhesive, it contains:
A) 90～94 weight % polyester diol, it is di-carboxylic acid component and C
2-6The polycondensation product of diol component, described di-carboxylic acid component comprise terephthalic acid and m-phthalic acid and non-essential C
6-12Aliphatic dicarboxylic acid unit, molecular weight are 27000-37500,
B) 6～10 weight % hyper-branched polyesters, described hyper-branched polyester is by 3,5-dihydroxyl C
1-2Alkylbenzene and 3, the copolymerization of 5-resorcylic acid forms, and 3,5-dihydroxyl C
1-2Alkylbenzene and 3, the mol ratio of 5-resorcylic acid are 1: 6～10, and the weight-average molecular weight that records with the gpc analysis method is 2000～4500.
2. composition of polyester hot-melt adhesive as claimed in claim 1, it is characterized in that in the total mole number of di-carboxylic acid component in the described polyester diol, the content of terephthalic acid units is 50～80 moles of %, the unitary content of m-phthalic acid is 10～40 moles of %, C
6-12The unitary content of aliphatic dicarboxylic acid is 0～20 mole of %.
3. composition of polyester hot-melt adhesive as claimed in claim 2, it is characterized in that in the total mole number of di-carboxylic acid component in the described polyester diol, the content of terephthalic acid units is 50～75 moles of %, the unitary content of m-phthalic acid is 10～35 moles of %, C
6-12The unitary content of aliphatic dicarboxylic acid is 10～20 moles of %.
4. as each described composition of polyester hot-melt adhesive in the claim 1～3, it is characterized in that described C
6-12Aliphatic dicarboxylic acid select 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
6-12The aliphatic dicarboxylic acid is a sebacic acid.
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 that is selected from ethylene glycol, propylene glycol, butyleneglycol, the hexylene glycol.
7. composition of polyester hot-melt adhesive as claimed in claim 1, it is characterized in that described hyper-branched polyester is by 3,5-orcin and 3, the copolymerization of 5-resorcylic acid forms, 3,5-orcin and 3, the mol ratio of 5-resorcylic acid are 1: 7～10, and the weight-average molecular weight that records with the gpc analysis method is 2000～3000.
8. composition of polyester hot-melt adhesive as claimed in claim 1 is characterized in that it contains nucleator and stablizer.
9. composition of polyester hot-melt adhesive as claimed in claim 1 is characterized in that, in the gross weight of this composition of polyester hot-melt adhesive, it contains the pure and mild 8 weight % hyper-branched polyesters of 92 weight % polyester binaries.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB2005101103383A CN1308410C (en) | 2005-11-14 | 2005-11-14 | Composition of polyester hot-melt adhesive in low melting viscosity |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB2005101103383A CN1308410C (en) | 2005-11-14 | 2005-11-14 | Composition of polyester hot-melt adhesive in low melting viscosity |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1760304A CN1760304A (en) | 2006-04-19 |
| CN1308410C true CN1308410C (en) | 2007-04-04 |
Family
ID=36706532
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CNB2005101103383A Expired - Fee Related CN1308410C (en) | 2005-11-14 | 2005-11-14 | Composition of polyester hot-melt adhesive in low melting viscosity |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN1308410C (en) |
Families Citing this family (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100439466C (en) * | 2007-06-29 | 2008-12-03 | 上海天洋热熔胶有限公司 | Polyester thermosol and preparation method thereof |
| CN101353562B (en) * | 2007-07-25 | 2012-01-25 | 比亚迪股份有限公司 | Preparation of polyester hot-melt adhesive |
| CN101434821B (en) * | 2007-11-16 | 2011-11-16 | 比亚迪股份有限公司 | Method for preparing hot-melt adhesive from polyester waste material |
| CN102492388B (en) * | 2011-11-30 | 2013-11-13 | 上海天洋热熔胶有限公司 | High-melting-point polyester hot melt adhesive with better fluidity |
| CN103184027B (en) * | 2011-12-28 | 2015-05-13 | 上海轻工业研究所有限公司 | Low-viscosity polyester hot melt adhesive and preparation method thereof |
| CN114517072B (en) * | 2022-03-10 | 2023-07-04 | 天津元汇科技有限公司 | Water-soluble degradable biomass hyperbranched citric acid polyester adhesive and application thereof |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4363853A (en) * | 1978-09-20 | 1982-12-14 | Asahi Kasei Kogyo Kabushiki Kaisha | Hot-melt polyester |
| US6114489A (en) * | 1997-03-27 | 2000-09-05 | Herberts Gmbh | Reactive hyperbranched polymers for powder coatings |
| US6255443B1 (en) * | 1998-07-13 | 2001-07-03 | Ems Chemie Ag | Low-melting copolyester and copolyetherester hot-melt adhesives |
| CN1340585A (en) * | 2000-08-29 | 2002-03-20 | 上海理日科技发展有限公司 | Process for preparing polyester thermosol with high smelting point |
-
2005
- 2005-11-14 CN CNB2005101103383A patent/CN1308410C/en not_active Expired - Fee Related
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4363853A (en) * | 1978-09-20 | 1982-12-14 | Asahi Kasei Kogyo Kabushiki Kaisha | Hot-melt polyester |
| US6114489A (en) * | 1997-03-27 | 2000-09-05 | Herberts Gmbh | Reactive hyperbranched polymers for powder coatings |
| US6255443B1 (en) * | 1998-07-13 | 2001-07-03 | Ems Chemie Ag | Low-melting copolyester and copolyetherester hot-melt adhesives |
| CN1340585A (en) * | 2000-08-29 | 2002-03-20 | 上海理日科技发展有限公司 | Process for preparing polyester thermosol with high smelting point |
Also Published As
| Publication number | Publication date |
|---|---|
| CN1760304A (en) | 2006-04-19 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN1308410C (en) | Composition of polyester hot-melt adhesive in low melting viscosity | |
| CN1142961C (en) | Polyesters including isosorbide as a comonomer and methods for making same | |
| US5681918A (en) | Process for preparing copolyesters of terephthalic acid ethylene glycol and 1 4-cyclohexanedimethanol exhibiting a neutral hue high clarity and increased brightness | |
| JPH0753464A (en) | Method of increasing rate of reaction of direct esterification of diacid with glycol | |
| CN101497775B (en) | Preparation of hydrolysis resisting polyester hot-melt adhesive | |
| CN1074429C (en) | Thermoplastic polyester continuous production process | |
| KR20120134937A (en) | Hydrolysis resistant and biodegradable aliphatic/aromatic copolyester resin composition | |
| CN106939076A (en) | The method for producing polyester | |
| US4499261A (en) | Process for the continuous production of polybutylene terephthalate of high molecular weight | |
| US6084055A (en) | Method for preparing poly(1,4-cyclohexanedicarboxylates) | |
| TW201422662A (en) | Continuous preparation method of biodegradable aliphatic/aromatic polyester copolymer | |
| CN1487964A (en) | Process for manufacture of polyesters based on 1,4-cyclohexanedimethanol and isophthalicacid | |
| JPH0567614B2 (en) | ||
| CN103184027B (en) | Low-viscosity polyester hot melt adhesive and preparation method thereof | |
| CN1962716A (en) | Low-melting point polyester synthesis method | |
| US4596886A (en) | Polyester containing impure 1,2-butanediol | |
| TW201422666A (en) | Continuous preparation method of biodegradable aliphatic/aromatic polyester copolymer | |
| JPH0429688B2 (en) | ||
| CN109666131B (en) | Preparation method of polybutylene terephthalate resin | |
| JP2023036861A (en) | Process for preparing poly(trimethylene furandicarboxylate) using zinc catalyst | |
| JPS6256173B2 (en) | ||
| JPH0931172A (en) | Polyester composition for plasticizer | |
| CN1796432A (en) | Polyesterglycol, adhesive of polyurethane and decorating plate of aluminum with high light film being covered | |
| CN103849348A (en) | Polyester hot melt adhesive composition and preparation method thereof | |
| CN1990809A (en) | Polyester thermosol and preparation method thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant | ||
| EE01 | Entry into force of recordation of patent licensing contract |
Assignee: Liri Chemical New Materials Co., Ltd. Shanghai Assignor: Shanghai Light Industry Research Institute Co., Ltd. Contract fulfillment period: 2007.4.4 to 2025.4.3 Contract record no.: 2008310000026 Denomination of invention: Composition of polyester hot-melt adhesive in low melting viscosity Granted publication date: 20070404 License type: Exclusive license Record date: 2008.9.9 |
|
| LIC | Patent licence contract for exploitation submitted for record |
Free format text: EXCLUSIVE LICENCE; TIME LIMIT OF IMPLEMENTING CONTACT: 2007.4.4 TO 2025.4.3 Name of requester: SHANGHAI LIRI NEW CHEMICAL MATERIALS CO., LTD. Effective date: 20080909 |
|
| TR01 | Transfer of patent right | ||
| TR01 | Transfer of patent right |
Effective date of registration: 20170605 Address after: 200031 Shanghai 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 City Baoqing Road No. 20 Patentee before: Shanghai Light Industry Research Institute Co., Ltd. |
|
| CF01 | Termination of patent right due to non-payment of annual fee | ||
| CF01 | Termination of patent right due to non-payment of annual fee |
Granted publication date: 20070404 Termination date: 20171114 |