CN105670546A - Polyether ester hot-melt adhesive and preparation method thereof - Google Patents
Polyether ester hot-melt adhesive and preparation method thereof Download PDFInfo
- Publication number
- CN105670546A CN105670546A CN201410652901.9A CN201410652901A CN105670546A CN 105670546 A CN105670546 A CN 105670546A CN 201410652901 A CN201410652901 A CN 201410652901A CN 105670546 A CN105670546 A CN 105670546A
- Authority
- CN
- China
- Prior art keywords
- copolymerization units
- acid
- aliphatic
- melt adhesive
- phthalic acid
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
Landscapes
- Polyesters Or Polycarbonates (AREA)
Abstract
The invention relates to a polyether ester hot-melt adhesive and a preparation method thereof. The polyether ester hot-melt adhesive contains a dicarboxylic acid copolymerization unit and a diol copolymerization unit, wherein the dicarboxylic acid copolymerization unit contains a phthalic acid copolymerization unit, a C2-C12 aliphatic dicarboxylic acid copolymerization unit and a C32-40 dimeric acid copolymerization unit, and the diol copolymerization unit contains a C2-C10 aliphatic diol copolymerization unit, a polyether diol copolymerization unit and a hydroxyalkyl modified organosilicon compound copolymerization unit. The polyether ester hot-melt adhesive disclosed by the invention has the advantages of low viscosity and excellent hydrolysis resistance, thermo-oxidative aging resistance and low-temperature flexibility, is particularly applicable to the adhered sealing of paper filter elements of automobile filters and the preparation of hot-melt adhesive films and can also be applied to the aspect of adhering of textiles.
Description
Technical field
The present invention relates to PUR and preparation method thereof, be specifically related to polyether ester PUR and preparation method thereof.
Background technology
In prior art, polyether ester is mostly for fibrous material and engineering plastics field, but also have for hotmelt field, such as patent CN96104247.8 (polyether ester for bonding of textiles), this patent obtains polyether ester by adopting addition polyalkylene ether glycols in common polyether ester PUR system to carry out copolymerization, although this patent solves the hot-air aging resistance of polyether ester by adding the mode of auxiliary agent; Just like patent CN201110388483.3 (a kind of polyether ester for bonding of textiles agent bonding), this patent adopts equally and adds polyalkylene ether glycols in traditional polyether ester thermosol formula to obtain polyether ester, the polyether ester of gained is be hardly damaged and fusing point decline in processing and grinding, it is easier to use.
In above patented technology, owing to polyether ester containing substantial amounts of ehter bond component, it is easy to thermo-oxidative ageing, and polyethers easily absorbs water, PUR deposit with use procedure in due to the effect of water cause hydrolysis generation, also result in PUR heating use procedure in produce a large amount of bubble and affect use.
Therefore, in the urgent need to the polyether ester PUR of a kind of low viscosity, hydrolytic resistance, heat oxygen aging resistance and low temperature flexibility excellence in this area.
Summary of the invention
The present invention adopts suitable modified monomer, is improved the defect of polyether ester PUR by the mode of copolymerization so that polyether ester PUR has low viscosity, hydrolytic resistance, heat oxygen aging resistance and good low temperature flexibility.
One aspect of the present invention provides a kind of polyether ester PUR, and it comprises:
(1) dicarboxylic acids copolymerization units, it includes:
(a) 60~100 moles of % phthalic acid copolymerization units;
(b) 0~20 mole of %C2-C12Aliphatic dicarboxylic acid copolymerization units; With
(c) 0~20 mole of %C32-40Dimeric dibasic acid copolymerization units, with the total mole number of dicarboxylic acids copolymerization units for benchmark; And
(2) diol copolymer unit, it includes:
(d) 84~99 moles of %C2-C10Aliphatic dihydroxy alcohol copolymerization units;
(e) 0~15 mole of % PTMEG copolymerization units,
The organo-silicon compound copolymerization units of f hydroxyalkyl groups that () 0.01-1 mole of % following formula represents, with the total mole number of diol copolymer unit for benchmark:
In formula, R is C2-4Alkylidene, n=1-100;The weight average molecular weight M of this polyester hot-melt adhesivewFor 2-10 ten thousand.
The preparation method that another aspect of the present invention provides above-mentioned polyether ester PUR, it comprises the steps:
A) phthalic acid or its C are provided1-4Ester, optional C2-10Aliphatic diacid or its C1-4Ester and C32-40Dimeric dibasic acid or its C1-4Ester and C2-8Aliphatic diol, the organo-silicon compound of the hydroxyalkyl groups represented with following formula and optional PTMEG:
In formula, R is C2-4Alkylidene, n=1-100, it is preferred to 4-65;
B) above-mentioned monomer mixture is made to be esterified at 180-220 DEG C of temperature under titanate catalyst exists; With
C) the monomer mixture polycondensation after the vacuum lower than 100Pa and 220-260 DEG C make esterification.
The polyether ester PUR copolymer that the present invention prepares has low viscosity and excellent hydrolytic resistance, heat oxygen aging resistance and low temperature flexibility, it is particularly well-suited to the paper filter core adhesive seal of automobile filter and for the preparation of hot melt adhesive film, it is possible to suitable in the application of bonding of textiles aspect.
Detailed description of the invention
In a preferred embodiment of the present invention, the polyester hot-melt adhesive of the present invention comprises:
(1) dicarboxylic acids copolymerization units, it includes:
(a) 70~95 moles of % phthalic acid copolymerization units;
(b) 0~15 mole of %C4-C8Aliphatic dicarboxylic acid copolymerization units; With
(c) 5~15 moles of %C34-38Dimeric dibasic acid copolymerization units, with the total mole number of dicarboxylic acids copolymerization units for benchmark; And
(2) diol copolymer unit, it includes:
(d) 89.5~95 moles of %C2-C8Aliphatic dihydroxy alcohol copolymerization units;
(e) 4.5~10 moles of % aliphatic polyether diol copolymerization units, and
The organo-silicon compound of f hydroxyalkyl groups that () 0.05-0.5 mole of % following formula represents, with the total mole number of diol copolymer unit for benchmark:
In formula, R is C2-4Alkylidene, n=4-65; The weight average molecular weight M of this polyester hot-melt adhesivewFor 2.5-5 ten thousand.
In a preferred embodiment of the present invention, the phthalic acid copolymerization units in polyester hot-melt adhesive of the present invention is derived by phthalic acid. Above-mentioned phthalic acid includes p-phthalic acid, M-phthalic acid and phthalic acid, it is preferred to p-phthalic acid, M-phthalic acid or their mixture. The mol ratio of p-phthalic acid and M-phthalic acid and/or phthalic acid is 70-100:0-30, it is preferable to 80-95:5-20, more preferably 85-95:5:15.
In a preferred embodiment of the present invention, the aliphatic dicarboxylic acid copolymerization units in polyester hot-melt adhesive of the present invention is by C2-C12Aliphatic dibasic acid is derivative and obtains, preferably by C4-C8Aliphatic dibasic acid is derivative and obtains. Above-mentioned C4-C8Aliphatic dicarboxylic acid is Straight chain diatomic acid, it is preferred that example includes one or more the mixture in 1, 4-succinic acid, 1,6-adipic acid, 1,8-suberic acid. In a particularly preferred embodiment, above-mentioned C in polyester hot-melt adhesive of the present invention2-C12The content of aliphatic dicarboxylic acid copolymerization units is 1~15 mole of %, with the total mole number of dicarboxylic acids copolymerization units for benchmark.
In a preferred embodiment of the present invention, above-mentioned C32-40Dimeric dibasic acid copolymerization units is by C16~20The dimer of unsaturated fatty acid is derivative and obtains. Above-mentioned dimeric dibasic acid is such as the dimeric dibasic acid derivative by linoleic acid, oleic acid, linolenic acid, elaidic acid, behenic acid, eleostearic acid or appropriate youngster's oil. Preferably C18The dimeric dibasic acid that unsaturated fatty acid is derivative, for instance, the dimerization such as appropriate youngster's oil, linoleic acid, oleic acid or linolenic acid the dimeric dibasic acid obtained, and the hydrogenated dimer acids obtained it is hydrogenated with by this dimeric dibasic acid.
Dimer acid material for the present invention requires that dimeric dibasic acid content is at more than 65wt%, it is preferable that 75~95wt%, three acid contents are at below 15wt%, it is preferable that 3~10wt%, mono-acid below content 5wt%, it is preferable that content is at 1~3wt%.
In a preferred embodiment of the present invention, above-mentioned C2-C10Aliphatic dihydroxy alcohol copolymerization units is derived by aliphatic dihydroxy alcohol and obtains. Above-mentioned aliphatic dihydroxy alcohol such as include ethylene glycol, BDO, neopentyl glycol, 1,6-hexanediol, 1,4-cyclohexanedimethanol or their mixture, it is preferably ethylene glycol, BDO, neopentyl glycol, 1,6-hexanediol or their mixture.
In a preferred embodiment of the present invention, above-mentioned aliphatic polyether diol copolymerization units is derived by aliphatic polyether diol and obtains, and above-mentioned aliphatic polyether diol includes by C1-4Aliphatic dihydric alcohol, it is preferable that by C2-4The PTMEG that aliphatic dihydric alcohol is polymerized, molecular weight is 200-6000, it is preferred to 800-4000. The example of aliphatic polyether diol includes but not limited to Polyethylene Glycol (PEG), PTMG (PTMEG), polypropylene glycol, it is preferable that Polyethylene Glycol.
In a preferred embodiment of the present invention, the organo-silicon compound of the hydroxyalkyl groups that the organo-silicon compound copolymerization units of above-mentioned hydroxyalkyl groups is represented by following formula (2) are derivative and obtain:
In formula, R is C2-4Alkylidene, n=1-100, it is preferred to 4-65. The molecular weight of these organo-silicon compound is preferably molecular weight 500-5000, is more preferably 800-3000.
In a preferred embodiment of the present invention, in polyester hot-melt adhesive of the present invention, the ratio of dicarboxylic acids copolymerization units total mole number and diol copolymer unit total mole number is 0.95~1.05:0.95~1.05, it is preferred to 1:1.
Although being not desired to be subject to concrete theoretical constraint, but inventor have found that can make gained polyester hot-melt adhesive have low viscosity and excellent hydrolytic resistance, heat oxygen aging resistance and low temperature flexibility by introducing the organo-silicon compound copolymerization units of above-mentioned hydroxyalkyl groups in polyester hot-melt adhesive molecular structure, is particularly well-suited to the application of bonding of textiles aspect.
The preparation method of polyester hot-melt adhesive of the present invention: above-mentioned binary acid, dihydroxylic alcohols carry out together esterification under the effect of catalyst, and the temperature range of reaction is 120~250 DEG C, it is preferred to 180~220 DEG C. In order to improve reaction conversion ratio and reach the ratio of above-mentioned dicarboxylic acids copolymerization units total mole number and diol copolymer unit total mole number, it is typically in reaction raw materials making the stoichiometry of dihydroxylic alcohols (particularly aliphatic dihydroxy alcohol) little over amount. Therefore, in a particularly preferred embodiment, in the reaction raw materials of polyester hot-melt adhesive of the present invention, above-mentioned binary acid is 1:(1.1~2.2 with total mol ratio of dihydroxylic alcohols), it is preferred to 1:(1.6~1.9).
Above-mentioned esterification can use catalyst conventional in the art, such as metatitanic acid alkane ester, it is preferred to metatitanic acid C1-5Arrcostab, such as metatitanic acid four methyl ester, tetraethyl titanate, metatitanic acid orthocarbonate, butyl titanate.
In the present invention, the consumption of catalyst is about 0.020~0.15 weight % of starting monomer gross weight, it is preferred to 0.025~0.1 weight %.
When the water distillated from reaction system reaches more than the 95% of theoretical amount, add polycondensation catalyst and thermal oxidation stabilizer, continue to gradually rise to 230~270 DEG C temperature, it is preferably 240-260 DEG C, apply to be less than about the vacuum of 100Pa, carry out polycondensation reaction, to remove water and the monomer of remnants from reaction system. After about 2~4 hours, obtain the melt with certain viscosity, stopped reaction, material is poured into while hot in cold water and cool down, obtain the copolyesters of the present invention.
Polycondensation catalyst still can with above-mentioned metatitanic acid alkane ester, and addition is about 0.02~0.10 weight % of starting monomer gross weight, it is preferred to 0.025~0.05 weight %.
Thermal oxidation stabilizer includes heat stabilizer and antioxidant.
The example of heat stabilizer includes phosphate ester and phosphite ester, and the example of phosphate ester includes trimethyl phosphate, triethyl phosphate, tributyl phosphate; The example of phosphite ester includes triphenyl phosphite, NSC 5284 and tributyl phosphite. The addition of heat stabilizer is about 0.020~0.10 weight % generating copolyesters gross weight, it is preferred to 0.025~0.05 weight %.
The example of antioxidant includes purchased from the IRGANOX1010 of Ciba company, IRGANOX245, IRGANOX1076, IRGANOX1098, IRGAFOX168, IRGAFOXB900, antioxidant 264 etc., the addition of antioxidant is about 0.02~1 weight % generating copolyesters gross weight, it is preferred to 0.05~1 weight %.
Above-mentioned reaction can also add additive commonly used in the art, such as nucleator, fire retardant etc. The example of nucleator includes Pulvis Talci, carboxylic acid sodium salt, ultra-fine or nano silicon etc. The addition of nucleator is generate 0.1~2 weight % of copolyesters gross weight, it is preferred to 0.1~1 weight %.
The fusing point of polyester hot-melt adhesive of the present invention is 130~210 DEG C, it is preferred to 160-200 DEG C, weight average molecular weight 2 ten thousand to 10 ten thousand, it is preferred to 2.5-5 ten thousand, not brittle failure under low temperature.
Embodiment:
Examples below is used for further illustrating the present invention, it is to be understood that these embodiments cannot be used for limiting the scope of the invention.
In each embodiment or comparative example, the polyether ester PUR of preparation tests various performance in accordance with the following methods:
Melt viscosity is tested: adopt BrookfieldDV-E type rotating cylinder viscometer test sample at the melt viscosity of 232 DEG C.
Specific viscosity is tested: adopt Ubbelohde viscometer method to carry out specific viscosity test by standard GB/T/T1632-93, for characterizing the size of its molecular weight, solvent for use is phenol tetrachloroethane (weight ratio is 1:1), survey synthetic specific viscosity more than 0.37
Fusing point and vitrification point test: DSC method is tested, after eliminating thermal history, heat up by 20 DEG C/min programming rate, test peak value (Tm) and the glass transition temperature (Tg) of its melting peak.
The bonding peel strength of canvas-canvas: adopt GB2791-81, draw speed 50mm/min.
The test of polyether ester PUR hydrolytic resistance and judgment criteria: polyether ester particle samples is placed in the hot bath of 80 DEG C and carries out the ageing-resistant test of decocting in water, take out after 12 hours and dry 3 hours in the baking oven of 100 DEG C, cool down when normal temperature drying, its specific viscosity of re-test, the fall % such as following formula of its specific viscosity can be tested, viscosity degradation amplitude is less than 15%, it is believed that this polyether ester has good hydrolytic resistance.
Viscosity degradation amplitude %=[(η0-η1)/η0] × 100%
η0The specific viscosity of sample before-hydrolysis process;
η1The specific viscosity of sample after-hydrolysis process.
Low-temperature flexibility is tested: reference standard HG/G4222-2011 hot melt adhesive cold flexibility test method, axle diameter used by flexure test is 12.8mm, and specimen size is 75mm (length) × 10mm (width) × 1.25mm (thickness).
Heatproof air aging performance is evaluated: is placed in by polyether ester in the baking oven of 230 DEG C and toasts after 5 hours, sample pours into 2mm slab-like, carrying out room temperature flexibility test, reference standard HG/G4222-2011 by the method for flexibility test after cooling, axle diameter used is 12.8mm.
Comparative example 1
P-phthalic acid 242g is added in a 2000ml stainless steel cauldron with thermometer, mechanical agitator, dephlegmator and condenser, M-phthalic acid 56g, 1,4-butanediol 300g, Polyethylene Glycol (reagent, molecular weight 2000) 40g, tetrabutyl titanate 0.23g, triphenyl phosphite 0.2g.Agitating heating heats up, when temperature in the kettle arrives 180-190 DEG C, esterification starts, and slowly promote temperature in the kettle to 220 DEG C, make to evaporate temperature and be maintained at 95-100 DEG C, collect the water that goes out of gold-plating to 64g, esterification terminates, add 5g antioxidant IRGONAX1010 and temperature is risen to 250 DEG C, open vacuum pump, polycondensation reaction is carried out under vacuum 100pa in still, reaction terminates rear discharging, the specific viscosity 0.37 recorded, weight average molecular weight 39750, melt viscosity 36800cps, fusing point 188 DEG C, glass transition temperature (Tg)-10 DEG C, canvas-canvas bonding strength 44N, hydrolysis tested viscosity fall is 35%, low-temperature flexibility test result is brittle failure at 25 DEG C of temperature, heatproof air aging performance test result is sample brittle failure.
Comparative example 2
P-phthalic acid 242g is added in a 2000ml stainless steel cauldron with thermometer, mechanical agitator, dephlegmator and condenser, M-phthalic acid 56g, 1,4-butanediol 300g, Polyethylene Glycol (reagent, molecular weight 2000) 30g, tetrabutyl titanate 0.23g, triphenyl phosphite 0.2g. agitating heating heats up, when temperature in the kettle arrives 180-190 DEG C, esterification starts, and slowly promote temperature in the kettle to 220 DEG C, make to evaporate temperature and be maintained at 95-100 DEG C, collect the water that goes out of gold-plating to 64g, esterification terminates, add 5g antioxidant IRGONAX1010 and temperature is risen to 250 DEG C, open vacuum pump, polycondensation reaction is carried out under vacuum 100pa in still, reaction terminates rear discharging, the specific viscosity 0.36 recorded, weight average molecular weight 32200, melt viscosity 38950cps, fusing point 189 DEG C, glass transition temperature (Tg)-12 DEG C, canvas-canvas bonding strength 34N, hydrolysis tested viscosity fall is 25%, low-temperature flexibility test result is brittle failure at 25 DEG C of temperature, heatproof air aging performance test result is sample brittle failure.
Embodiment 1
P-phthalic acid 242g is added in a 2000ml stainless steel cauldron with thermometer, mechanical agitator, dephlegmator and condenser, M-phthalic acid 12g, 1,4-butanediol 300g, Polyethylene Glycol (reagent, molecular weight 2000) 40g, dimeric dibasic acid (CrodaPripol1013) 152g, the end hydroxyalkyl groups organo-silicon compound (Tech-2120 of Shanghai Tag polymer company limited, molecular weight 2000) 4g, tetrabutyl titanate 0.23g, triphenyl phosphite 0.2g. agitating heating heats up, when temperature in the kettle arrives 180-190 DEG C, esterification starts, and slowly promote temperature in the kettle to 220 DEG C, make to evaporate temperature and be maintained at 95-100 DEG C, collect the water that goes out of gold-plating to 64g, esterification terminates, add 5g antioxidant IRGONAX1010 and temperature is risen to 250 DEG C, open vacuum pump, polycondensation reaction is carried out under vacuum 100pa in still, reaction terminates rear discharging, the specific viscosity 0.39 recorded, weight average molecular weight 31000, melt viscosity 21500cps, fusing point 190 DEG C, glass transition temperature (Tg)-28 DEG C, canvas-canvas bonding strength 43N, hydrolysis tested viscosity fall is 10%, low-temperature flexibility test result is not brittle failure at-15 DEG C of temperature, heatproof air aging performance test result is sample not brittle failure.
Embodiment 2
P-phthalic acid 242g is added in a 2000ml stainless steel cauldron with thermometer, mechanical agitator, dephlegmator and condenser, M-phthalic acid 30g, 1,4-butanediol 300g, Polyethylene Glycol (reagent, molecular weight 2000) 40g, dimeric dibasic acid (CrodaPripol1013) 91g, the end hydroxyalkyl groups organo-silicon compound (Tech-2120 of Shanghai Tag polymer company limited, molecular weight 2000) 4g, tetrabutyl titanate 0.23g, triphenyl phosphite 0.2g.Agitating heating heats up, when temperature in the kettle arrives 180-190 DEG C, esterification starts, and slowly promote temperature in the kettle to 220 DEG C, make to evaporate temperature and be maintained at 95-100 DEG C, collect the water that goes out of gold-plating to 64g, esterification terminates, add 5g antioxidant IRGONAX1010 and temperature is risen to 250 DEG C, open vacuum pump, polycondensation reaction is carried out under vacuum 100pa in still, reaction terminates rear discharging, the specific viscosity 0.38 recorded, weight average molecular weight 28200, melt viscosity 24530cps, fusing point 188 DEG C, glass transition temperature (Tg)-25 DEG C, canvas-canvas bonding strength 34N, hydrolysis tested viscosity fall is 8%, low-temperature flexibility test result is not brittle failure at-15 DEG C of temperature, heatproof air aging performance test result is sample not brittle failure.
Embodiment 3
P-phthalic acid 242g is added in a 2000ml stainless steel cauldron with thermometer, mechanical agitator, dephlegmator and condenser, M-phthalic acid 48g, 1,4-butanediol 300g, Polyethylene Glycol (reagent, molecular weight 2000) 40g, dimeric dibasic acid (CrodaPripol1013) 97g, the end hydroxyalkyl groups organo-silicon compound (Tech-2120 of Shanghai Tag polymer company limited, molecular weight 2000) 4g, tetrabutyl titanate 0.23g, triphenyl phosphite 0.2g. agitating heating heats up, when temperature in the kettle arrives 180-190 DEG C, esterification starts, and slowly promote temperature in the kettle to 220 DEG C, make to evaporate temperature and be maintained at 95-100 DEG C, collect the water that goes out of gold-plating to 64g, esterification terminates, add 5g antioxidant IRGONAX1010 and temperature is risen to 250 DEG C, open vacuum pump, polycondensation reaction is carried out under vacuum 100pa in still, reaction terminates rear discharging, the specific viscosity 0.37 recorded, weight average molecular weight 35700, melt viscosity 20600cps, fusing point 180 DEG C, glass transition temperature (Tg)-26 DEG C, canvas-canvas bonding strength 30N, hydrolysis tested viscosity fall is 7%, low-temperature flexibility test result is not brittle failure at-15 DEG C of temperature, heatproof air aging performance test result is sample not brittle failure.
Embodiment 4-7
Method is consistent with embodiment 1, and summary table formula and performance are shown in following table.
Claims (10)
1. a polyether ester PUR, it comprises:
(1) dicarboxylic acids copolymerization units, it includes:
(a) 60~100 moles of % phthalic acid copolymerization units;
(b) 0~20 mole of %C2-C12Aliphatic dicarboxylic acid copolymerization units; With
(c) 0~20 mole of %C32-40Dimeric dibasic acid copolymerization units, with the total mole number of dicarboxylic acids copolymerization units for benchmark; And
(2) diol copolymer unit, it includes:
(d) 84~99 moles of %C2-C10Aliphatic dihydroxy alcohol copolymerization units;
(e) 0~15 mole of % PTMEG copolymerization units,
The organo-silicon compound copolymerization units of f hydroxyalkyl groups that () 0.01-1 mole of % following formula represents, with the total mole number of diol copolymer unit for benchmark:
In formula, R is C2-4Alkylidene, n=1-100; The weight average molecular weight M of this polyester hot-melt adhesivewFor 2-10 ten thousand.
2. polyester hot-melt adhesive as claimed in claim 1, it is characterised in that it comprises:
(1) dicarboxylic acids copolymerization units, it includes:
(a) 70~95 moles of % phthalic acid copolymerization units;
(b) 0~15 mole of %C4-C8Aliphatic dicarboxylic acid copolymerization units; With
(c) 5~15 moles of %C34-38Dimeric dibasic acid copolymerization units, with the total mole number of dicarboxylic acids copolymerization units for benchmark; And
(2) diol copolymer unit, it includes:
(d) 89.5~95 moles of %C2-C8Aliphatic dihydroxy alcohol copolymerization units;
(e) 4.5~10 moles of % aliphatic polyether glycol copolymerization units, and
The organo-silicon compound copolymerization units of f hydroxyalkyl groups that () 0.05-0.5 mole of % following formula represents:
In formula, R is C2-4Alkylidene, n=4-65, with the total mole number of diol copolymer unit for benchmark; The weight average molecular weight M of this polyester hot-melt adhesivewFor 2.5-5 ten thousand.
3. polyester hot-melt adhesive as claimed in claim 1 or 2, it is characterised in that described phthalic acid is p-phthalic acid, M-phthalic acid or their mixture.
4. polyester hot-melt adhesive as claimed in claim 1 or 2, it is characterised in that described C32-40Dimeric dibasic acid is C16~20The dimer of unsaturated fatty acid.
5. polyester hot-melt adhesive as claimed in claim 1 or 2, it is characterised in that described PTMEG includes by C1-4The PTMEG that aliphatic dihydric alcohol is polymerized, molecular weight is 200-6000, it is preferred to 800-4000.
6. the preparation method of the polyether ester PUR as described in any one of claim 1-5, it comprises the steps:
A) phthalic acid, optional C are provided2-10Aliphatic diacid and C32-40Dimeric dibasic acid and C2-8Aliphatic diol, the organo-silicon compound of the hydroxyalkyl groups represented with following formula and optional PTMEG:
In formula, R is C2-4Alkylidene, n=1-100, it is preferred to 4-65;
B) above-mentioned monomer mixture is made to be esterified at 180-220 DEG C of temperature under titanate catalyst exists; With
C) the monomer mixture polycondensation after the vacuum lower than 100Pa and 220-260 DEG C make esterification.
7. preparation method as claimed in claim 6, it is characterised in that include phthalic acid, optional C2-10Aliphatic diacid and C32-40The total acid of dimeric dibasic acid with include C2-8The mol ratio of total alcohol of aliphatic diol, the organo-silicon compound of hydroxyalkyl groups and optional PTMEG is 1:1.1-2.2, it is preferable to 1:1.6-1.9.
8. preparation method as claimed in claims 6 or 7, it is characterised in that the mol ratio of p-phthalic acid and M-phthalic acid and/or phthalic acid is 70-100:0-30, it is preferred to 80-95:5-20, more preferably 85-95:5:15.
9. preparation method as claimed in claims 6 or 7, it is characterised in that described titanate catalyst is metatitanic acid C1-5Arrcostab.
10. preparation method as claimed in claims 6 or 7, it is characterised in that be additionally added phosphite ester stabilizer in step b), adds antioxidant in step c).
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CN201410652901.9A CN105670546A (en) | 2014-11-17 | 2014-11-17 | Polyether ester hot-melt adhesive and preparation method thereof |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CN201410652901.9A CN105670546A (en) | 2014-11-17 | 2014-11-17 | Polyether ester hot-melt adhesive and preparation method thereof |
Publications (1)
Publication Number | Publication Date |
---|---|
CN105670546A true CN105670546A (en) | 2016-06-15 |
Family
ID=56944058
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
CN201410652901.9A Pending CN105670546A (en) | 2014-11-17 | 2014-11-17 | Polyether ester hot-melt adhesive and preparation method thereof |
Country Status (1)
Country | Link |
---|---|
CN (1) | CN105670546A (en) |
Cited By (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN107325272A (en) * | 2017-07-11 | 2017-11-07 | 南通协鑫热熔胶有限公司 | A kind of semiaromatic type polyester hot-melt adhesive of the block containing silicone macromolecule and preparation method thereof |
CN109293908A (en) * | 2017-11-20 | 2019-02-01 | Sk化学公司 | Hot melt adhesive polyester and resin composition |
CN109708978A (en) * | 2018-12-29 | 2019-05-03 | 北京东方雨虹防水技术股份有限公司 | A kind of low temperature flexibility test method suitable for waterproof hot-fusible pressure-sensitive adhesive |
CN114015403A (en) * | 2021-09-27 | 2022-02-08 | 苏州赛伍应用技术股份有限公司 | Polyurethane adhesive, hot-pressing insulating film prepared from polyurethane adhesive and application of polyurethane adhesive |
Citations (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN101240060A (en) * | 2007-01-26 | 2008-08-13 | 赢创德固赛有限责任公司 | Crystalline copolyesters having good solubility in unhalogenated solvents and their use |
CN101497775A (en) * | 2008-02-02 | 2009-08-05 | 上海轻工业研究所有限公司 | Preparation of hydrolysis resisting polyester hot-melt adhesive |
-
2014
- 2014-11-17 CN CN201410652901.9A patent/CN105670546A/en active Pending
Patent Citations (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN101240060A (en) * | 2007-01-26 | 2008-08-13 | 赢创德固赛有限责任公司 | Crystalline copolyesters having good solubility in unhalogenated solvents and their use |
CN101497775A (en) * | 2008-02-02 | 2009-08-05 | 上海轻工业研究所有限公司 | Preparation of hydrolysis resisting polyester hot-melt adhesive |
Cited By (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN107325272A (en) * | 2017-07-11 | 2017-11-07 | 南通协鑫热熔胶有限公司 | A kind of semiaromatic type polyester hot-melt adhesive of the block containing silicone macromolecule and preparation method thereof |
CN109293908A (en) * | 2017-11-20 | 2019-02-01 | Sk化学公司 | Hot melt adhesive polyester and resin composition |
CN109708978A (en) * | 2018-12-29 | 2019-05-03 | 北京东方雨虹防水技术股份有限公司 | A kind of low temperature flexibility test method suitable for waterproof hot-fusible pressure-sensitive adhesive |
CN109708978B (en) * | 2018-12-29 | 2021-09-07 | 北京东方雨虹防水技术股份有限公司 | Low-temperature flexibility testing method suitable for waterproof hot-melt pressure-sensitive adhesive |
CN114015403A (en) * | 2021-09-27 | 2022-02-08 | 苏州赛伍应用技术股份有限公司 | Polyurethane adhesive, hot-pressing insulating film prepared from polyurethane adhesive and application of polyurethane adhesive |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
CN112566990B (en) | Polyester resin composition, powder coating and workpiece | |
CN105670546A (en) | Polyether ester hot-melt adhesive and preparation method thereof | |
CN102282211B (en) | Polyester resin composition, process for production of same, and film | |
TWI774879B (en) | Polyester resin composition for a hot melt adhesive | |
TWI811422B (en) | Liquid crystal polyester resin for laminate, liquid crystal polyester resin composition, laminate, liquid crystal polyester resin film, and method for producing laminate and liquid crystal polyester resin film | |
JP2006096955A (en) | Aromatic liquid crystalline polyester film | |
KR20100020915A (en) | Polyester for producing fiber, and fiber and non-woven fabric using the same | |
CN104105770A (en) | Vegetable oil-based pressure-sensitive adhesives | |
CN107325272A (en) | A kind of semiaromatic type polyester hot-melt adhesive of the block containing silicone macromolecule and preparation method thereof | |
CN104629663A (en) | Polyester hot melt adhesive | |
CN103184027B (en) | Low-viscosity polyester hot melt adhesive and preparation method thereof | |
CN108299632A (en) | A kind of liquid crystal polyester and its application | |
CN101759961A (en) | Hydrolysis-resistance polyester composition and preparation method there | |
JP2013032424A (en) | Copolymerized polyester resin, and coating material and adhesive using the same | |
CN104334642A (en) | Polymer composition | |
CN104448271A (en) | Lactic-acid-based branched aliphatic polyester and preparation method thereof | |
TWI249543B (en) | Crosslinked polyester copolymers | |
JP2012001688A (en) | Copolyester resin and adhesive using the same | |
CN108239509B (en) | Polyether ester hot melt adhesive with good heat resistance and preparation method thereof | |
JP5643072B2 (en) | Liquid crystal polyester | |
CN103897646B (en) | Resistant to hydrolysis polyester hot-melt adhesive and preparation method thereof | |
CN104726049A (en) | Modified low-melting-point polyester hot melt adhesive, and preparation method thereof | |
JP6464747B2 (en) | Polyester resin and water dispersion using the same | |
CN103849348B (en) | A kind of composition of polyester hot-melt adhesive and preparation method thereof | |
CN105061741A (en) | Water-boiling-resistant polyester resin 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 | ||
WD01 | Invention patent application deemed withdrawn after publication | ||
WD01 | Invention patent application deemed withdrawn after publication |
Application publication date: 20160615 |