CN103849348A - Polyester hot melt adhesive composition and preparation method thereof - Google Patents
Polyester hot melt adhesive composition and preparation method thereof Download PDFInfo
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- CN103849348A CN103849348A CN201210516646.6A CN201210516646A CN103849348A CN 103849348 A CN103849348 A CN 103849348A CN 201210516646 A CN201210516646 A CN 201210516646A CN 103849348 A CN103849348 A CN 103849348A
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Abstract
The invention relates to a polyester hot melt adhesive composition and a preparation method thereof. The polyester hot melt adhesive composition comprises: (a) polyester diol which is a condensation polymerization product of a dicarboxylic acid component and a dihydric alcohol component with 2-6 carbon atoms, and (b) fatty acid strontium with 16-20 carbon atoms, wherein the dicarboxylic acid component comprises terephthalic acid, unnecessary isophthalic acid and an aliphatic dicarboxylic acid unit with 4-12 carbon atoms, and the weight-average molecular weight of the dicarboxylic acid component is 10,000-100,000. The polyester hot melt adhesive composition has very high fluidity and fusing 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 and the efficiency that apply.The good fluidity of glue, coating or forming process temperature are low, less energy consumption, surface covered and quality might as well; The poor fluidity of glue, perviousness, spreadability when coating are also poor, have not only increased the consumption of glue, have also affected adhesiveproperties.Owing to being high-temperature fusion coating, also require polyester hot-melt adhesive to there is good melt stability.
Prior art is to add flow ability modifying agent to carry out screw rod blend in the major measure aspect raising polyester mobility.For production of polyester enterprise, screw rod blend has increased operation and cost, has affected 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 composition of polyester hot-melt adhesive of a kind of good fluidity and 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 di-carboxylic acid component and C
2-6the polycondensation product of diol component, described di-carboxylic 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
4-12di-carboxylic acid component and the C of aliphatic dicarboxylic acid and m-phthalic acid
2-6diol component carries out polycondensation, and
2) in polycondensation product, add C
16-20lipid acid strontium.
The present invention is by using C
16-20lipid acid strontium carries out modification to polyester diol, makes the synthetic polyester hot-melt adhesive obtaining have high mobility, has good melt stability and bonding strength, the low cost of manufacture of this high flow polyester hot-melt adhesive composition, easily coating simultaneously.
Embodiment
One preferred embodiment in, 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 contains 30～90 % by mole of terephthalic acid units, 5～45 % by mole of m-phthalic acid unit and 5～45 % by mole of C
6-10aliphatic dicarboxylic acid unit, taking the total mole number of di-carboxylic acid component in described polyester diol as benchmark.
In a preferred embodiment, described polyester diol contains 50～80 % by mole of terephthalic acid units, 10～30 % by mole of m-phthalic acid unit and 10～30 % by mole of C
6-10aliphatic dicarboxylic acid unit, taking the total mole number of di-carboxylic acid component in described polyester diol as benchmark.
Above-mentioned terephthalic acid, m-phthalic acid and C
4-12aliphatic dicarboxylic acid unit can be by terephthalic acid, m-phthalic acid and C
4-12aliphatic dicarboxylic acid or their C
1-4alkyl ester produces.
C
4-12aliphatic dicarboxylic acid's example 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 being selected from ethylene glycol, propylene glycol, butyleneglycol, pentanediol, hexylene glycol.Above-mentioned dibasic alcohol can use separately, also can two or more mix use.
One preferred embodiment in, 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, can make the polycondensation together with under the effect of diol component at catalyzer of above-mentioned dibasic acid 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, for example, 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 under normal pressure, also can reduce pressure down and carry out.In the time that water outlet reaches theoretical value 95%, esterification finishes.Continue to be warming up to 240 ~ 260 ° of C, under the condition that vacuumizes decompression step by step, carry out copolycondensation, make 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, obtains composition of polyester hot-melt adhesive of the present invention.
One preferred embodiment in, 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.
In above-mentioned transesterification reaction, can use catalyzer conventional in this area, as metatitanic acid alkane ester, as metatitanic acid tetramethyl ester, tetraethyl titanate, metatitanic acid orthocarbonate, tetrabutyl titanate.
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.
In the time that the alcohol distillating from transesterification reaction system reaches theoretical amount, in the time that the water distillating from esterification system reaches theoretical amount, continue temperature to be increased to gradually 240 ~ 260 ° of C, apply the vacuum that is less than about 133Pa, carry out polycondensation, to remove remaining water and monomer from reaction system.For preventing reactant discharge system, vacuumize and answer proceed step by step, proceed to high vacuum from rough vacuum gradually.The overbottom pressure of final system is lower than 133Pa.
In polycondensation reaction system, can add catalyzer and stablizer.
Polycondensation catalyst still can be with above-mentioned metatitanic acid alkane ester, and add-on is about 0.01 ~ 0.15 % by weight that forms 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 ° below C.Then in this reaction mixture, add C
16-20lipid acid strontium and other optional additive, as stablizer and nucleator, oxidation inhibitor, tinting material, weighting agent etc.After stirring, cooling, pelletizing, makes 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 finishes, by cooling gained reaction product, with gel chromatography (GPC) method mensuration (weight average) molecular weight.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 for example can be referring to CN1990810A.
The preparation method of composition of polyester hot-melt adhesive of the present invention can directly blend in reactor, has advantages of that production efficiency is high, production cost is low.
The composition of polyester hot-melt adhesive making 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 embodiment can not be used for limiting the scope of the invention.Protection scope of the present invention is limited by appending claims.
The polyester hot-melt adhesive making in each embodiment and comparative example test performance in accordance with the following methods:
Mobility: the melt viscosity by test polyester is evaluated, and under uniform temp, melt viscosity is lower, and mobility is better.
Melting heat stability: polyester hot-melt adhesive is placed 6 hours in 230 DEG C of DEG C of baking ovens, tested the value of specific viscosity after 6 hours, 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: the 11g polyester hot-melt adhesive sample of accurately weighing, in baking oven, dry moisture, adopt the test of Brookfield DV-E type rotational viscosimeter, probe temperature is 230 DEG C, rotor S27, record the rotor melt viscosity value that dial plate shows after 30min that runs up, rotating speed is adjusted according to practical situation.
Specific viscosity test: by standard GB/T/T1632-93, 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: adopt the DSC-823c test of Mettler, through twice intensification scanning, heating rate is 20 DEG C/min, and the melting peak temperature heating up is for the second time fusing point.
Embodiment 1
Lean on thermometer, mechanical stirrer, fractionation at one with the 1L reactor of condenser in add 1,234 grams of 4-butyleneglycols, under agitation add 232.4 grams of terephthalic acids immediately, 33.2 grams of m-phthalic acids, 58.4 grams of hexanodioic acids, and 0.23 gram of the positive ethyl ester of phthalandione.Heat temperature raising, in the time being warmed up to 170 DEG C of left and right, starts to distillate water droplet, heats up in a steamer 90～100 DEG C of temperature, continues heating direct to temperature in the kettle and reaches 220 DEG C of left and right, and in the time that water quantity of distillate reaches theoretical amount, esterification completes, and obtains low-molecular-weight oligopolymer.Continue temperature to rise to 240～250 DEG C of left and right, and improve the vacuum tightness of system, until the vacuum tightness of system is less than 133Pa.In the time that polycondensation power reaches preset value, be filled with nitrogen and remove vacuum to normal pressure, add 3.4 grams of strontium stearates (purchased from too chemical company of upper hamming), continue to stir 20 minutes, while hot molten materials is poured in cold water, obtain white adhesive tape, be cut into micelle, obtain composition of polyester hot-melt adhesive of the present invention.
Dry after 6 hours at 100 DEG C, 176 DEG C of the fusing points recording, specific viscosity is 0.39, melt viscosity is 20800mPa.S/230 DEG C.The melting in 230 DEG C of baking ovens of dried polyester hot-melt adhesive particle was placed after 6 hours, and testing its specific viscosity is 0.36.
Embodiment 2,3 and 4
Above three embodiment 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
Lean on thermometer, mechanical stirrer, fractionation at one with the 1L reactor of condenser in add 1,234 grams of 4-butyleneglycols, under agitation add 232.4 grams of terephthalic acids immediately, 33.2 grams of m-phthalic acids, 58.4 grams of hexanodioic acids, and 0.23 gram of the positive ethyl ester of phthalandione.Heat temperature raising, in the time being warmed up to 170 DEG C of left and right, starts to distillate water droplet, heats up in a steamer 90～100 DEG C of temperature, continues heating direct to temperature in the kettle and reaches 220 DEG C of left and right, and in the time that water quantity of distillate reaches theoretical amount, esterification completes, and obtains low-molecular-weight oligopolymer.Continue temperature to rise to 240～250 DEG C of left and right, and improve the vacuum tightness of system, until the vacuum tightness of system is less than 133Pa.In the time that 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.
Dry after 6 hours at 100 DEG C, 176 DEG C of the fusing points recording, specific viscosity is 0.39, melt viscosity is 31300mPa.S/230 DEG C.The melting in 230 DEG C of baking ovens of dried polyester hot-melt adhesive particle was placed after 6 hours, and 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.
Formula and the analytical results of the each embodiment of table 1 and comparative example
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 for adopting the example of strontium stearate modification, and comparative example 1,2 is not for adopting the example of properties-correcting agent, and comparative example 3,4 is respectively the example that adopts properties-correcting agent calcium stearate and Zinic stearas.
Can be clear that by the data in table, in embodiment 1,2,3,4 gained polyester hot-melt adhesives, add after strontium stearate blend, mixture melt viscosity obviously declines, and flowing property improves greatly; Comparative example 1 and 2 do not add strontium stearate melt viscosity apparently higher than embodiment 1 and 2, comparative example 3 and 4 adopt respectively calcium stearate and Zinic stearas modification reduce melt viscosity effect not as embodiment 3,4 obvious.
As can also be seen from Table 1, embodiment 1,2,3,4 gained polyester hot-melt adhesives, place after 6 hours through 230 DEG C of meltings, and the rate of descent of its specific viscosity is less than respectively the specific viscosity rate of descent of comparative example 1,2,3,4 gained polyester hot-melt adhesives.This explanation, embodiment 1,2,3,4 gained polyester hot-melt adhesives have 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 to say, polyester hot-melt adhesive of the present invention degradation speed under molten state is slower, and this is obviously more favourable to melt coating, does not worry that hot melt adhesive degrades too fast and affect coating quality and cohesive strength in molten groove.
Surprisingly, by the composition of polyester hot-melt adhesive of the present invention that adds strontium stearate and polyester hot-melt adhesive blend to obtain, not only there is better mobility in reactor, and there is better thermostability under molten state.And add the salt such as calcium stearate, Zinic stearas of the same type, 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, without any peculiar smell, therefore production efficiency is high, production cost is low.
Claims (10)
1. a composition of polyester hot-melt adhesive for high workability, it comprises:
A) polyester diol, it is di-carboxylic acid component and C
2-6the polycondensation product of diol component, described di-carboxylic 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.
2. composition of polyester hot-melt adhesive as claimed in claim 1, is characterized in that, in the total mole number of di-carboxylic 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
4-12aliphatic dicarboxylic acid's content is 0～70 % by mole.
3. composition of polyester hot-melt adhesive as claimed in claim 2, is characterized in that, in the total mole number of di-carboxylic 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
6-10aliphatic dicarboxylic acid's content is 5～45 % by mole.
4. the composition of polyester hot-melt adhesive as described in any one in claim 1～3, is characterized in that, described C
4-12aliphatic 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
5-12aliphatic dicarboxylic acid select 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 being 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 accounts for 0.1 ~ 5 % by weight of polyester diol composition total weight, preferably accounts for 0.3 ~ 2 % by weight.
8. the composition of polyester hot-melt adhesive as described in claim 1 or 7, is characterized in that, described C
16-20lipid acid strontium is C
16-20saturated fatty acid strontium.
9. the composition of polyester hot-melt adhesive as described in claim 1 or 7, is characterized in that, described C
16-20lipid acid strontium is strontium stearate.
10. the preparation method of composition of polyester hot-melt adhesive as claimed in any one of claims 1-9 wherein, it comprises the steps:
1) make to comprise terephthalic acid and non-essential C
4-12di-carboxylic acid component and the C of aliphatic dicarboxylic acid and m-phthalic acid
2-6diol component carries out polycondensation, and
2) in polycondensation product, add C
16-20lipid acid strontium.
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Cited By (2)
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| CN104479116A (en) * | 2014-12-04 | 2015-04-01 | 金发科技股份有限公司 | Preparation method of poly-terephthalic acid isophthalic acid adipic acid/ butanediol copolyester |
| CN105566616A (en) * | 2014-10-15 | 2016-05-11 | 中国石油化工股份有限公司 | Copolyester preparation method and application of copolyester prepared thereby in 3 D printing |
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| US20050107576A1 (en) * | 2002-02-14 | 2005-05-19 | Hideshi Hori | 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 |
| CN102732202A (en) * | 2012-06-16 | 2012-10-17 | 上海天洋热熔胶有限公司 | Preparation method for non-crystalline low-melting point polyester hot melt adhesive |
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| CN1476459A (en) * | 2000-11-30 | 2004-02-18 | ����贻�ѧ��ҵ��ʽ���� | Aliphatic polyester copolymer and process for producing same, biodegradable resin molding based on aliphatic polyester, and lactone-containing resin |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN105566616A (en) * | 2014-10-15 | 2016-05-11 | 中国石油化工股份有限公司 | Copolyester preparation method and application of copolyester prepared thereby in 3 D printing |
| CN105566616B (en) * | 2014-10-15 | 2018-09-21 | 中国石油化工股份有限公司 | A kind of application of copolyesters preparation method and gained copolyesters in 3D printing |
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