CN1990809B - Polyester thermosol and preparation method thereof - Google Patents
Polyester thermosol and preparation method thereof Download PDFInfo
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- CN1990809B CN1990809B CN2005101121485A CN200510112148A CN1990809B CN 1990809 B CN1990809 B CN 1990809B CN 2005101121485 A CN2005101121485 A CN 2005101121485A CN 200510112148 A CN200510112148 A CN 200510112148A CN 1990809 B CN1990809 B CN 1990809B
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Abstract
The invention provides a polyester hot melt adhesive, comprising following components: (a) 15-85 wt% of oligomerization phthalic acid C2-C6 alkylidene ester with a weight-average molecular weight between 1100-4400; (b) 15-85 wt% of oligomerization C2-C8 alkylidene dicarboxylic acid C2-C6 alkylidene ester with the weight- average molecular weight between 1000- 4000, and the weight-average molecular weight of said polyester hot melt adhesive being 20000-35000 based on a total weigth of the polyester hot melt adhesive. The method for preparing the polyester hot melt adhesive comprises following steps: (1) mixing phthalic acid C1-C4 alkyl ester and C2-C6 alkylidene diol according to an alcohol and acid molar ratio of 1.7- 2.0: 1, heating to 100-250 DEG C for a transesterification; (2) continuously heating to a temperature of 250-260 DEG C for a polycondensation and obtaining the oligomerization phthalic acid C2-C6 alkylidene ester with the weight-average molecular weight between 1100-4400; (3) adding the oligomerization C2-C8 alkylidene dicarboxylic acid C2- C6 alkylidene ester with the weight-average molecular weight between 1000-4000 into the reaction system, continuously stirring and heating to 240-260 DEG C for the polycondensation. The polyester hot melt adhesive has characteristics of high melting point and good flowability.
Description
Technical field
The present invention relates to polyester hot-melt adhesive and preparation method thereof, relate more specifically to block polyester hot melt adhesive and preparation method thereof.
Background technology
Present polyester hot-melt adhesive both domestic and external all adopts aromatic acid (or its dimethyl ester) such as terephthalic acid and long carbochain aliphatic dibasic acid (or its dimethyl ester), dibasic alcohol, earlier through esterification (or transesterify), obtain after the polycondensation then.
Because aromatic acid is different with the reactive behavior of aliphatic dibasic acid, reaction conditions is restive, and the reaction times is longer.The fusing point of the random polyester that obtains is lower, and dystectic bonding purposes is difficult to satisfy the demand.
Summary of the invention
The object of the present invention is to provide a kind of new polyester hot-melt adhesive and preparation method thereof.The fusing point and the flowability of this polyester hot-melt adhesive are greatly improved, and its polyreaction characteristics of having that condition is controlled easily, the reaction times is short, cost is low etc.
Polyester hot-melt adhesive of the present invention comprises:
A) 15～85 weight % oligomerisation phthalic acid C
2-C
6Alkylene ester, its weight-average molecular weight be 1100～4400 and
B) 15～85 weight % oligomerisation C
2～C
8Alkylene dicarboxylic acids C
2～C
6Alkylene ester, its weight-average molecular weight are 1000～4000, are benchmark with the gross weight of polyester hot-melt adhesive,
The weight-average molecular weight of described polyester hot-melt adhesive is 20000～35000.
Preparation method of polyester hot melt adhesive of the present invention comprises the steps:
I) by 1.7～2.0: 1 molar ratio of alcohol to acid pure mixed phthalic acid C
1-C
4Alkane ester and C
2-C
6Aklylene glycol is heated to 100～250 ℃ and carries out transesterification reaction;
Ii) continue to heat up 250～260 ℃ and carries out polycondensation, obtain weight-average molecular weight and be 1100～4400 oligomerisation phthalic acid C
2-C
6Alkylene ester,
Iii) in reaction system, add weight-average molecular weight and be 1000～4000 oligomerisation C
2～C
8Alkylene dicarboxylic acids C
2～C
6Alkylene ester continues to be heated with stirring to 240～260 ℃, carries out polycondensation.
Description of drawings
Fig. 1 is mole the figure that % did of the fusing point of polyester to terephthalic acid units in the polyester.
Fig. 2 is that the fusing point of polyester is to synthetic used hexanodioic acid monomer, the oligomerisation hexanodioic acid 1 of this copolyesters, the figure that the weight-average molecular weight of 4-butanediol ester is done.
Fig. 3 represents a preferred implementation of the reaction path of polyester hot-melt adhesive of the present invention.
Fig. 4 represents the conventional preparation method's of a typical polyester hot-melt adhesive reaction path.
Embodiment
Polyester hot-melt adhesive of the present invention comprises 15～85 weight % oligomerisation phthalic acid C
2-C
6Alkylene ester and 15～85 weight % oligomerisation C
2～C
8Alkylene dicarboxylic acids C
2～C
6Alkylene ester preferably comprises the described oligomerisation phthalic acid of 30～70 weight % C
2-C
6Alkylene ester and the described oligomerisation C of 30～70 weight %
2～C
8Alkylene dicarboxylic acids C
2～C
6Alkylene ester is a benchmark with the gross weight of polyester hot-melt adhesive.Polyester hot-melt adhesive of the present invention is most preferably by the described oligomerisation phthalic acid of 30～70 weight % C
2-C
6Alkylene ester and the described oligomerisation C of 30～70 weight %
2～C
6Alkylene dicarboxylic acids C
2～C
6Alkylene ester is formed.
The weight-average molecular weight of polyester hot-melt adhesive of the present invention is 20000～35000, is preferably 25000～33000.
The fusing point of polyester hot-melt adhesive of the present invention is generally 120～200 ℃, is preferably 130～200 ℃, and melt viscosity is 18500～33000cp, is preferably 19000～21000.
The synthetic method of polyester hot-melt adhesive of the present invention comprises three steps, i.e. a step transesterification reaction and the reaction of two one-step polycondensations.
In transesterification reaction, used phthalic acid C
1-C
4The alkane ester comprises the C of terephthalic acid, m-phthalic acid, phthalic acid or their mixtures
1-C
4The alkane ester preferably includes the C of terephthalic acid, m-phthalic acid or their mixtures
1-C
4Alkane ester, most preferably terephthalic acid C
1-C
4The alkane ester.
Phthalic acid C
1-C
4The alkane ester is by phthalic acid and C
1-C
4Alkanol makes.C
1-C
4Alkanol comprises methyl alcohol, ethanol, propyl alcohol, butanols or their mixture, preferably includes methyl alcohol, ethanol or their mixture, most preferably methyl alcohol.
In transesterification reaction, used C
2-C
6Alkylene alcohol comprises ethylene glycol, propylene glycol, butyleneglycol, pentanediol, hexylene glycol or their mixture, preferably includes 1,4-butyleneglycol, 1,6-hexylene glycol or their mixture, most preferably 1,4-butyleneglycol.
C
2-C
6The mol ratio of alkylene alcohol and phthalic acid is 1.7～2.0: 1, is preferably 1.8～2.0: 1.
Transesterification reaction is generally pressed above-mentioned acid-alcohol ratio with phthalic acid C by method preparation as known in the art
1-C
4Alkane ester and C
2-C
6Alkylene alcohol mixes together, is heated to 100～250 ℃ and carries out transesterification reaction, distillates C from reaction system
1-C
4Alkanol.
The temperature of transesterification reaction is preferably 130～210 ℃.This transesterification reaction can be carried out under normal pressure, also can under reduced pressure carry out, but vacuum tightness should not be hanged down reactant and obviously discharged degree in the reaction system.
Above-mentioned reaction system is continued to be heated to 250～280 ℃, carry out the first step polycondensation, obtain oligomerisation phthalic acid C
2-C
6Alkylene ester.
Gained oligomerisation phthalic acid C
2-C
6The weight-average molecular weight of alkylene ester is 1100～4400, is preferably 2200～3300.Its hydroxyl value is preferably 25～102mgKOH/g, more preferably 34～51mgKOH/g.
The temperature of polycondensation is preferably 250～260 ℃, and this polycondensation can be carried out under normal pressure, also can under reduced pressure carry out, but vacuum tightness should not be hanged down the degree that reactant is obviously discharged reaction system, and vacuum tightness is generally less than 133Pa.
Proceed to the oligomerisation phthalic acid C that obtains required weight-average molecular weight when the first step polycondensation
2-C
6Behind the alkylene ester, reaction system is cooled off a little, added oligomerisation C in proportion
2～C
8Alkylene dicarboxylic acids C
2～C
6Alkylene ester is heated to reaction system 250～280 ℃ again, preferred 250～260 ℃, carries out the reaction of second one-step polycondensation.
The reaction of second one-step polycondensation can be carried out under the temperature and pressure identical with the first step polycondensation.
The C that adds in the reaction of second one-step polycondensation
2～C
8Alkylene dicarboxylic acids C
2～C
6Alkylene ester can be by known method preparation or commercially available.
Oligomerisation C
2～C
8Alkylene dicarboxylic acids C
2～C
6The example of alkylene ester comprises the oligomerisation EGS ethylene glycol succinate, oligomerisation Succinic Acid propylene glycol ester, the oligomerisation succinic acid-butanediol ester, oligomerisation Succinic Acid pentadiol ester, oligomerisation Succinic Acid hexylene glycol ester, the oligomerisation EGG ethylene glycol glutarate, oligomerisation pentanedioic acid propylene glycol ester, oligomerisation pentanedioic acid butanediol ester, oligomerisation pentanedioic acid pentadiol ester, oligomerisation pentanedioic acid hexylene glycol ester, the oligomerisation ethylene glycol adipate(EGA), oligomerisation hexanodioic acid propylene glycol ester, the oligomerisation tetramethylene adipate, oligomerisation hexanodioic acid pentadiol ester, oligomerisation hexanodioic acid hexylene glycol ester, oligomerisation pimelic acid glycol ester, oligomerisation pimelic acid propylene glycol ester, oligomerisation pimelic acid butanediol ester, oligomerisation pimelic acid pentadiol ester, oligomerisation pimelic acid hexylene glycol ester, oligomerisation suberic acid glycol ester, oligomerisation suberic acid propylene glycol ester, oligomerisation suberic acid butanediol ester, oligomerisation suberic acid pentadiol ester, oligomerisation suberic acid hexylene glycol ester, oligomerisation sebacic acid glycol ester, oligomerisation sebacic acid propylene glycol ester, oligomerisation sebacic acid butanediol ester, oligomerisation sebacic acid pentadiol ester, oligomerisation sebacic acid hexylene glycol ester or their mixture.
Preferred oligomerisation C
2～C
6Alkylene dicarboxylic acids C
2～C
6Alkylene ester comprises oligomerisation EGS ethylene glycol succinate, oligomerisation succinic acid-butanediol ester, oligomerisation Succinic Acid hexylene glycol ester, oligomerisation ethylene glycol adipate(EGA), oligomerisation tetramethylene adipate, oligomerisation hexanodioic acid hexylene glycol ester, or their mixture.
Most preferred oligomerisation C
2～C
4Alkylene dicarboxylic acids C
2～C
6Alkylene ester comprises oligomerisation hexanodioic acid 1,4-butanediol ester, oligomerisation hexanodioic acid 1,4-hexylene glycol ester, or their mixture.
Used oligomerisation C among the present invention
2～C
6Alkylene dicarboxylic acids C
2～C
6The weight-average molecular weight of alkylene ester is 1000～4000, is preferably 2000～3000.Its hydroxyl value is preferably 28～112mgKOH/g, more preferably 37～56mgKOH/g.
In polyester hot-melt adhesive of the present invention, also can comprise monomer commonly used in some this areas, as chain extension agent.
Can use catalyzer conventional in this area in above-mentioned transesterify and the polycondensation, as metatitanic acid alkane ester, as metatitanic acid tetramethyl ester, tetraethyl titanate, metatitanic acid orthocarbonate, tetrabutyl titanate or their mixture.
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 %.
Can add stablizer in esterification and the polycondensation reaction system.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.
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 %.
In a preferred implementation, polyester hot-melt adhesive of the present invention is synthetic by reaction path shown in Figure 3.
After polycondensation finishes, the gained reaction product is cooled off, adopt the Ubbelohde viscometer method to carry out the mensuration of viscosity ratio increment by standard GB/T 1632-93, be used to characterize its molecular weight size, solvent for use is phenol-tetrachloroethane (weight ratio is 1: 1), and the synthetics viscosity ratio increment that records is greater than 0.37.
Adopt the DSC test
Heat analysis is adopted the DSC testing method, fusing point, the cooling curing temperature of test polyester hot-melt adhesive, and heating curve heats up with 20 ℃/min temperature rise rate, and temperature lowering curve is with the rate of temperature fall cooling of 5 ℃/min.
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, temperature is controlled at 160 ℃, and constantly regulate and rotate rotating speed, make its test value be positioned at the linearity range of 10-90%, observed value is write down in stable back.
A kind of conventional preparation method of typical polyester hot-melt adhesive is undertaken by reaction path shown in Figure 4.
In above-mentioned conventional preparation method, the dimethyl terephthalate (DMT) warp is with 1, and after the exchange of 4-butanediol ester, direct and binary aliphatic acid mono carries out esterification, polycondensation, obtains random polyester hot-melt adhesive.This conventional preparation method's long reaction time, productive rate are low, and the cost height can not obtain the sufficiently high polyester hot-melt adhesive of fusing point.
Embodiment
Embodiment 1
Have thermometer, mechanical stirrer at one, fractionation is leant on the 1000ml stainless steel cauldron of condenser in add dimethyl terephthalate (DMT) 170 grams, 1, the positive ethyl ester 0.20 of 4-butyleneglycol 158 grams and phthalandione restrains.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 60-70 ℃, 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, continue to be warming up to 250-260 ℃, carry out decompression vacuum pumping with vacuum pump,, remove vacuum when power of agitator reaches 90-95W power.The sample that takes a morsel from reactor is measured its weight-average molecular weight by above-mentioned method, is 2200～3300, hydroxyl value 40mgKOH/g.
Add poly-hexanodioic acid 1 while hot, (molecular weight is 1000 to 4-butanediol ester 175g, hydroxyl value 28mgKOH/g, be full of polymer technology Development Co., Ltd available from Shanghai connection), continue to heat up, stir, carry out decompression vacuum pumping again with vacuum pump during to 240-250 ℃, the vacuum tightness that keeps reaction system continues reaction and promptly finished polycondensation in about 2 hours less than 133Pa.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.
Drying is after 24 hours down at 50 ℃, and 120 ℃ of the fusing points that records, melt viscosity 200pa.s (200 ℃), viscosity ratio increment are 0.36, and weight-average molecular weight is 28000.
Embodiment 2-8
Below Shi Yan processing method is identical with embodiment 1, and used prescription result is as shown in table 1 below:
Table 1
Comparative Examples 9
Have thermometer, mechanical stirrer at one, fractionation is leant on the 1000ml stainless steel cauldron of condenser in add dimethyl terephthalate (DMT) 194 grams, 1, the positive ethyl ester 0.23 of 4-butyleneglycol 450 grams and phthalandione restrains.Heat temperature raising when temperature in the kettle reaches 130 ℃, 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 60-70 ℃, 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, cooling.
Below temperature drop to 100 in the aforesaid reaction vessel ℃, promptly add hexanodioic acid 216 grams, and adding triphenyl phosphite 0.2 gram, stir then and heat up, when about interior temperature rise to 160 ℃, there is water to distillate, heat up in a steamer temperature and be generally 90-105 ℃, continue to be warming up to about 210 ℃, the water quantity of distillate continued progressively temperature to be risen to about 245～250 ℃ greater than 98% o'clock of theoretical value, carried 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 80 ℃ dry 12 hours, measure 112 ℃ of fusing points, 200 ℃ of following melt viscosities are 18500cp, and the viscosity ratio increment is 0.36, and weight-average molecular weight is 28000.
Comparative Examples 10-13
Below Shi Yan processing method is identical with Comparative Examples 9, and used prescription result is as shown in table 2 below:
Table 2
Annotate: wherein Suan Mole% calculates with the amount of total acid, and used alcohol is 1,4 butyleneglycol in synthesizing, and the consumption of alcohol/acid is 2/1.
Fig. 1 represents mole the figure that % did of the fusing point of polyester hot-melt adhesive to terephthalic acid units in this copolyesters.Fig. 1 clearly illustrates that, adopts block fashion synthetic polyester hot-melt adhesive of the present invention higher 5～10 ℃ than the fusing point of the atactic polyester that has identical mol ratio with random copolymerization mode synthetic.
Fig. 2 represents that the fusing point of polyester hot-melt adhesive is to synthetic used hexanodioic acid monomer, the oligomerisation hexanodioic acid 1 of this copolyesters, the figure that the weight-average molecular weight of 4-butanediol ester is done.Fig. 2 clearly illustrates that the fusing point of block polyester hot melt adhesive of the present invention is more much higher than the fusing point of the random polyester hot-melt adhesive with identical mol ratio.And, under identical mole proportioning, the oligomerisation hexanodioic acid 1 of block fashion synthetic copolyesters of the present invention will be adopted, the weight-average molecular weight of 4-butanediol ester is high more, its fusing point is also high more, for example be 4000 oligomerisation hexanodioic acid 1 with weight-average molecular weight, the fusing point of the polyester of 4-butanediol ester preparation exceeds 18 ℃ than random copolymers fusing point.
The higher polyester hot-melt adhesive of fusing point must guarantee that again polyester hot-melt adhesive has the user of good fluidity simultaneously for the needs good heat resistance, has certain meaning.
On the other hand, under identical fusing point, adopt hexanodioic acid molar weight used in the random copolymerization method synthetic copolyester hot melt adhesive less than adopting used hexanodioic acid molar weight in the block method synthetic copolyester hot melt adhesive, be that soft segment in the segmented copolymer is more, the mobile enhancing, in table 1 and table 2, be under 170 ℃ the situation at fusing point, fusing point viscosity under 200 ℃ of the random synthetic copolyester hot melt adhesives is 32500cp, the melt viscosity that block synthetic copolyester hot melt adhesive is 200 ℃ is 19800cp, reduces about 40%.
Claims (10)
1. polyester hot-melt adhesive, it comprises:
A) 15～85 weight % oligomerisation phthalic acid C
2-C
6Alkylene ester, its weight-average molecular weight be 1100～4400 and
B) 15～85 weight % oligomerisation C
2～C
8Alkylene dicarboxylic acids C
2～C
6Alkylene ester, its weight-average molecular weight are 1000～4000, are benchmark with the gross weight of polyester hot-melt adhesive,
The weight-average molecular weight of described polyester hot-melt adhesive is 20000～35000.
2. polyester hot-melt adhesive as claimed in claim 1 is characterized in that it comprises the described oligomerisation phthalic acid of 30～70 weight % C
2-C
6Alkylene ester and the described oligomerisation C of 30～70 weight %
2～C
8Alkylene dicarboxylic acids C
2～C
6Alkylene ester is a benchmark with the gross weight of polyester hot-melt adhesive.
3. polyester hot-melt adhesive as claimed in claim 1 is characterized in that described oligomerisation phthalic acid C
2-C
6Alkylene ester comprises oligomerisation terephthalic acid 1,4-butanediol ester, oligomerisation m-phthalic acid 1,4-butanediol ester and their mixture.
4. polyester hot-melt adhesive as claimed in claim 1 is characterized in that described oligomerisation C
2～C
8Alkylene dicarboxylic acids C
2～C
6Alkylene ester comprises oligomerisation hexanodioic acid 1,4-butanediol ester, oligomerisation hexanodioic acid 1,6-hexylene glycol ester and their mixture.
5. polyester hot-melt adhesive as claimed in claim 1, the weight-average molecular weight that it is characterized in that described polyester hot-melt adhesive is 25000～33000.
6. polyester hot-melt adhesive as claimed in claim 1 is characterized in that described oligomerisation phthalic acid C
2-C
6The hydroxyl value of alkylene ester is 25～102mgKOH/g, described oligomerisation C
2～C
8Alkylene dicarboxylic acids C
2～C
6The hydroxyl value of alkylene ester is 28～112mgKOH/g.
7. preparation method of polyester hot melt adhesive as claimed in claim 1, it comprises the steps:
I) by 1.7～2.0: 1 molar ratio of alcohol to acid pure mixed phthalic acid C
1-C
4Alkane ester and C
2-C
6Aklylene glycol is heated to 100～250 ℃ and carries out transesterification reaction;
Ii) continue to heat up 250～260 ℃ and carries out polycondensation, obtain weight-average molecular weight and be 1100～4400 oligomerisation phthalic acid C
2-C
6Alkylene ester,
Iii) in reaction system, add weight-average molecular weight and be 1000～4000 oligomerisation C
2～C
8Alkylene dicarboxylic acids C
2～C
6Alkylene ester continues to be heated with stirring to 240～260 ℃, carries out polycondensation.
8. preparation method as claimed in claim 7 is characterized in that described transesterification reaction carries out in the presence of titanic acid ester.
9. as claim 7 or 8 described preparation methods, it is characterized in that described polycondensation carries out in the presence of titanic acid ester.
10. preparation method as claimed in claim 7 is characterized in that described transesterification reaction and polycondensation carry out in the presence of phosphoric acid ester or phosphorous acid ester.
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|---|---|---|---|
| CN2005101121485A CN1990809B (en) | 2005-12-28 | 2005-12-28 | Polyester thermosol and preparation method thereof |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2005101121485A CN1990809B (en) | 2005-12-28 | 2005-12-28 | Polyester thermosol and preparation method thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
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| CN1990809B true CN1990809B (en) | 2011-05-04 |
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Country Status (1)
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Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN86104826A (en) * | 1986-07-19 | 1987-09-23 | 天津化学纤维研究所 | Modified polyester fiber and preparation method |
| 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
- 2005-12-28 CN CN2005101121485A patent/CN1990809B/en not_active Expired - Fee Related
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN86104826A (en) * | 1986-07-19 | 1987-09-23 | 天津化学纤维研究所 | Modified polyester fiber and preparation method |
| 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 |
Non-Patent Citations (1)
| Title |
|---|
| US 6,255,443 B1,2001.07.03,说明书全文. |
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|---|---|
| CN1990809A (en) | 2007-07-04 |
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