CN101864264A - Solvent-type polyurethane flocking adhesive and preparation method thereof - Google Patents
Solvent-type polyurethane flocking adhesive and preparation method thereof Download PDFInfo
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- CN101864264A CN101864264A CN 201010195482 CN201010195482A CN101864264A CN 101864264 A CN101864264 A CN 101864264A CN 201010195482 CN201010195482 CN 201010195482 CN 201010195482 A CN201010195482 A CN 201010195482A CN 101864264 A CN101864264 A CN 101864264A
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- polyester diol
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- 238000002360 preparation method Methods 0.000 title claims abstract description 45
- 239000000853 adhesive Substances 0.000 title claims abstract description 44
- 230000001070 adhesive effect Effects 0.000 title claims abstract description 44
- 229920002635 polyurethane Polymers 0.000 title claims abstract description 33
- 239000004814 polyurethane Substances 0.000 title claims abstract description 33
- 238000005886 esterification reaction Methods 0.000 claims abstract description 61
- 229920000642 polymer Polymers 0.000 claims abstract description 36
- 238000006068 polycondensation reaction Methods 0.000 claims abstract description 23
- 238000006243 chemical reaction Methods 0.000 claims abstract description 14
- 239000007787 solid Substances 0.000 claims abstract description 13
- WERYXYBDKMZEQL-UHFFFAOYSA-N butane-1,4-diol Chemical compound OCCCCO WERYXYBDKMZEQL-UHFFFAOYSA-N 0.000 claims abstract description 12
- NSOXQYCFHDMMGV-UHFFFAOYSA-N Tetrakis(2-hydroxypropyl)ethylenediamine Chemical compound CC(O)CN(CC(C)O)CCN(CC(C)O)CC(C)O NSOXQYCFHDMMGV-UHFFFAOYSA-N 0.000 claims abstract description 11
- XXMIOPMDWAUFGU-UHFFFAOYSA-N hexane-1,6-diol Chemical compound OCCCCCCO XXMIOPMDWAUFGU-UHFFFAOYSA-N 0.000 claims abstract description 11
- QQVIHTHCMHWDBS-UHFFFAOYSA-N isophthalic acid Chemical compound OC(=O)C1=CC=CC(C(O)=O)=C1 QQVIHTHCMHWDBS-UHFFFAOYSA-N 0.000 claims abstract description 11
- 238000002156 mixing Methods 0.000 claims abstract description 6
- 229920000728 polyester Polymers 0.000 claims description 98
- 150000002009 diols Chemical class 0.000 claims description 57
- 230000032050 esterification Effects 0.000 claims description 57
- 230000015572 biosynthetic process Effects 0.000 claims description 43
- 238000003786 synthesis reaction Methods 0.000 claims description 43
- WOZVHXUHUFLZGK-UHFFFAOYSA-N dimethyl terephthalate Chemical compound COC(=O)C1=CC=C(C(=O)OC)C=C1 WOZVHXUHUFLZGK-UHFFFAOYSA-N 0.000 claims description 40
- 239000002994 raw material Substances 0.000 claims description 29
- 239000000178 monomer Substances 0.000 claims description 20
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 claims description 20
- 229920002554 vinyl polymer Polymers 0.000 claims description 20
- 238000000034 method Methods 0.000 claims description 17
- 238000005086 pumping Methods 0.000 claims description 16
- 239000002253 acid Substances 0.000 claims description 13
- 239000003795 chemical substances by application Substances 0.000 claims description 13
- 238000010792 warming Methods 0.000 claims description 10
- UPMLOUAZCHDJJD-UHFFFAOYSA-N 4,4'-Diphenylmethane Diisocyanate Chemical compound C1=CC(N=C=O)=CC=C1CC1=CC=C(N=C=O)C=C1 UPMLOUAZCHDJJD-UHFFFAOYSA-N 0.000 claims description 9
- 244000144992 flock Species 0.000 claims description 9
- 150000002148 esters Chemical class 0.000 claims description 6
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 6
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 5
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 abstract 6
- NIQCNGHVCWTJSM-UHFFFAOYSA-N Dimethyl phthalate Chemical compound COC(=O)C1=CC=CC=C1C(=O)OC NIQCNGHVCWTJSM-UHFFFAOYSA-N 0.000 abstract 2
- FBSAITBEAPNWJG-UHFFFAOYSA-N dimethyl phthalate Natural products CC(=O)OC1=CC=CC=C1OC(C)=O FBSAITBEAPNWJG-UHFFFAOYSA-N 0.000 abstract 1
- 229960001826 dimethylphthalate Drugs 0.000 abstract 1
- 238000007711 solidification Methods 0.000 abstract 1
- 230000008023 solidification Effects 0.000 abstract 1
- 230000002194 synthesizing effect Effects 0.000 abstract 1
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 9
- 230000003068 static effect Effects 0.000 description 7
- 239000000835 fiber Substances 0.000 description 5
- 150000001412 amines Chemical group 0.000 description 3
- 150000007520 diprotic acids Chemical class 0.000 description 3
- AVWRKZWQTYIKIY-UHFFFAOYSA-N urea-1-carboxylic acid Chemical group NC(=O)NC(O)=O AVWRKZWQTYIKIY-UHFFFAOYSA-N 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- 239000003292 glue Substances 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- -1 timber Polymers 0.000 description 2
- ZTNJGMFHJYGMDR-UHFFFAOYSA-N 1,2-diisocyanatoethane Chemical compound O=C=NCCN=C=O ZTNJGMFHJYGMDR-UHFFFAOYSA-N 0.000 description 1
- NIXOWILDQLNWCW-UHFFFAOYSA-N Acrylic acid Chemical compound OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 1
- 230000001464 adherent effect Effects 0.000 description 1
- 238000005034 decoration Methods 0.000 description 1
- 239000000428 dust Substances 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 229920001971 elastomer Polymers 0.000 description 1
- 230000005684 electric field Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 239000004744 fabric Substances 0.000 description 1
- 238000000227 grinding Methods 0.000 description 1
- 239000010985 leather Substances 0.000 description 1
- 238000012423 maintenance Methods 0.000 description 1
- 238000012856 packing Methods 0.000 description 1
- 239000000123 paper Substances 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 239000005060 rubber Substances 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
Landscapes
- Polyurethanes Or Polyureas (AREA)
- Adhesives Or Adhesive Processes (AREA)
Abstract
The invention discloses a solvent-type polyurethane flocking adhesive and a preparation method thereof, which belong to the field of adhesives. The flocking adhesive is prepared according to the following steps: preparing polyesterdiol: mixing dimethyl phthalate and 1, 4-butanediol for carrying out primary esterification reaction; adding m-phthalic acid and 1, 6-hexanediol for carrying out secondary esterification reaction after the primary esterification reaction; and carrying out polycondensation reaction on a reaction system after the secondary esterification reaction to obtain the polyesterdiol; synthesizing performed polymers: preparing the performed polymers through mixing the prepared polyesterdiol with 4, 4' methyl diphenylene diisocyanate and ethyl acetate; and carrying out secondary chain extension: dripping the prepared performed polymers into quadrol and ethyl acetate to obtain the adhesive with the solid content between 35 and 45 percent and the viscosity between 4000 and 7000 mPa*s, i.e. the solvent-type polyurethane flocking adhesive. The solvent-type polyurethane flocking adhesive has the excellent body performance, and has the advantages of high initial stick force in an operatable range, high solidification speed and the like, and the dryness and humidity resistance firmness can reach more than 10000 times.
Description
Technical field
The present invention relates to the adhesive glue field, particularly relate to a kind of solvent-type polyurethane flocking adhesive and preparation method thereof.
Background technology
Employed tackiness agent when static flocking adhesive is meant static flocking.With fiber dust (by useless fiber by grinding or cut off the staple fibre that obtains, length is generally 0.03～0.5 centimetre) vertical fixing (as plastics, timber, rubber, leather, paper, cloth etc.) on object that scribbles tackiness agent or base material, this staple fibre fixed method is called flocking.Industrial employing mainly contain two kinds of machinery, static, at present based on static flocking.Static flocking is on the bar-shaped electrode of staple fibre fine hair in electric field because after electrostatic effect obtains an electric charge, can move to and correspondingly extremely go up, because dipole nature, fine hair can be arranged in rows as the direction of power line, and it is, bonding and fixing by means of tackiness agent perpendicular to corresponding substrate surface.
Flock printed article has obtained widespread use in industries such as clothes town, packing, decoration, shoemaking, and wherein PVC mantle and PVC leatheroid are the flock printed article large usage quantity of base material, and development rapidly.The static flocking tackiness agent mainly is that acrylic ester adhesive is used morely in the market, but the adherent fastness is relatively poor, and general dried wet rubbing fastness is about 2000～4000 times, and the life-span of using this flock printed article to make product can't guarantee.
Summary of the invention
The purpose of the embodiment of the invention provides a kind of solvent-type polyurethane flocking adhesive and preparation method thereof, overcomes existing vinylformic acid and plants that the melten gel initial bonding strength is low, the shortcoming of Bearable dry and wet wipe poor performance, and a kind of high performance solvent-type polyurethane flocking adhesive is provided.
The objective of the invention is to be achieved through the following technical solutions:
The embodiment of the invention provides a kind of solvent-type polyurethane flocking adhesive, and this Flock Adhesive is prepared from by following step:
Preparation polyester diol: by mass percentage, dimethyl terephthalate (DMT) with 25～35%, 15～30% 1,4 butyleneglycols, 15～30% m-phthalic acid and 20～30% 1,6 hexylene glycols are raw material, dimethyl terephthalate (DMT) and the mixing of 1,4 butyleneglycol are carried out esterification one time, add m-phthalic acid and 1 after the esterification, 6 hexylene glycols carry out the secondary esterification, and the reaction system after the secondary esterification is carried out making polyester diol after the polycondensation;
Synthetic performed polymer: by mass percentage, the above-mentioned polyester diol that makes with 35～45%, 10～15% 4,4 ' diphenylmethanediisocyanate and 35～50% vinyl acetic monomer are raw material, to make performed polymer after the above-mentioned polyester diol that makes and 4,4 ' diphenylmethanediisocyanate and the vinyl acetic monomer mixing;
Secondary chain extension: by mass percentage, the above-mentioned performed polymer that makes with 60～70%, 1～5% quadrol and 20～40% vinyl acetic monomer are raw material, the above-mentioned performed polymer that makes is dropped in quadrol and the vinyl acetic monomer, make solid content and be 35%～45%, viscosity is the tackiness agent of 4000～7000mPas, is solvent-type polyurethane flocking adhesive.
The embodiment of the invention also provides a kind of preparation method of solvent-type polyurethane flocking adhesive, comprising:
The preparation polyester diol, used each raw material is all by mass percentage in this preparation polyester diol step:
An esterification:
Dimethyl terephthalate (DMT) with 25～35%, 15～30% 1,4 butyleneglycol join and are warming up to 210～230 ℃ in the polyester synthesis reactor, react 2～3 hours, finish an esterification;
The secondary esterification:
Be warming up to 210～230 ℃ after in the reaction system of the above-mentioned polyester synthesis reactor of finishing an esterification, adding 15～30% m-phthalic acid, 20～30% 1,6 hexylene glycol, reacted 5～6 hours, finish the secondary esterification;
Polycondensation:
To taking out rough vacuum in the above-mentioned polyester synthesis reactor of finishing after the secondary esterification, vacuum tightness from-0.02Mpa～-0.04Mpa, take out rough vacuum and stop after 2～3 hours, put overhead product;
To pumping high vacuum in the above-mentioned polyester synthesis reactor of taking out after rough vacuum is finished, vacuum tightness from-0.05Mpa～-0.09Mpa, the pumping high vacuum time is 2.5～3.5 hours, the still temperature control of polyester synthesis reactor is at 245 ℃～255 ℃ in the pumping high vacuum process;
After pumping high vacuum finishes, grow in the polyester synthesis reactor and vacuumize, vacuum tightness will reach-0.094Mpa; The long pumpdown time is 6～8 hours, puts overhead product, and overhead product accounts for 5～15% of the raw materials used total mass of preparation polyester diol, and length vacuumizes the aftercondensated reaction and finishes, and the product of polycondensation is polyester diol;
Synthetic performed polymer, used each raw material is all by mass percentage in this synthetic performed polymer step:
Make solid content after the polyester diol that above-mentioned preparation polyester diol step with 35～45% makes, 4,4 ' diphenylmethanediisocyanate of 10～15%, 35～50% vinyl acetic monomer mix and be 50%～65%, isocyano-content is 3～5% performed polymer;
Secondary chain extension, used each raw material is all by mass percentage in this secondary chain extension step:
The performed polymer that makes in 60～70% the above-mentioned synthetic performed polymer step is dropped in the vinyl acetic monomer of 1～5% quadrol and 20～40%, the dropping time is 0.5～1 hour, make solid content and be 35%～45%, viscosity is the tackiness agent of 4000～7000mPas, is solvent-type polyurethane flocking adhesive.
The technical scheme that provides by the invention described above embodiment as can be seen, in the embodiment of the invention by in reasonably combined with crystallinity dibasic alcohol and amorphism diprotic acid of the synthesis phase of preparation polyester diol, and in follow-up secondary chain extension process, introduce an amount of allophanate groups, the molecule segment two ends are with reactive amines group end-blocking, make this solvent-type polyurethane flocking adhesive have excellent body performance, but in operating restraint, has the initial bonding strength height, advantages such as curing speed is fast, its Bearable dry and wet wipe fastness can reach more than 10000 times.
Embodiment
The invention will be further described below in conjunction with specific embodiment.
Embodiment 1
Present embodiment provides a kind of solvent-type polyurethane flocking adhesive, and this Flock Adhesive is to be prepared from by following method, specifically comprises:
(1) preparation polyester diol, by mass percentage, the dimethyl terephthalate (DMT) with 25～35%, 15～30% 1,4 butyleneglycol, 15～30% m-phthalic acid and 20～30% 1,6 hexylene glycol are as the raw material of preparation polyester diol;
Preparation process is as follows:
(1) esterification:
The dimethyl terephthalate (DMT) of 25～35% in the above-mentioned prescription, 15～30% 1,4 butyleneglycol joined in the polyester synthesis reactor mix, the polyester synthesis reactor is warming up to 210～230 ℃, reacted 2～3 hours, finish an esterification;
In the esterification process, keeping the alcohol amount to be stabilized in per hour is 1.5～3% of the raw materials used total mass of preparation polyester diol, distillates methyl alcohol and is generally 5～10%;
(2) secondary esterification:
In the reaction system of the above-mentioned polyester synthesis reactor of finishing an esterification, add 15～30% m-phthalic acid, 20～30% 1,6 hexylene glycol and be warming up to 210～230 ℃, reacted 5～6 hours, finish the secondary esterification;
In the secondary esterification process, keep that the aquifer yield of polyester synthesis reactor is stable per hour to be 1～1.5% hour of the raw materials used total mass of preparation polyester diol; Treat that esterification finishes, determine by the acid number≤20mgKOH/g that measures product whether esterification is qualified;
(3) polycondensation:
To taking out rough vacuum in the above-mentioned polyester synthesis reactor of finishing after the secondary esterification, vacuum tightness is-0.02Mpa～-0.04Mpa, take out rough vacuum after 2～3 hours, stop to take out rough vacuum by the vacuum line valve of cutting off the polyester synthesis reactor, put overhead product;
Continuation is to pumping high vacuum in the above-mentioned polyester synthesis reactor that stops to take out after the rough vacuum, vacuum tightness from-0.05Mpa～-0.09Mpa, taking out the high time is 2.5～3.5h, the still temperature control of polyester synthesis reactor is at 245 ℃～255 ℃; After pumping high vacuum finishes, vacuumize growing in the polyester synthesis reactor by the Luoci pump that starts the polyester synthesis reactor, vacuum tightness will reach-0.094Mpa, long finding time is 6～8 hours, put overhead product, overhead product accounts for 5～15% of preparation polyester diol raw materials used total mass, behind the bunching should after the bunching product that obtains be polyester diol;
Further, also can should confirm whether to have made qualified polyester diol behind the bunching by hydroxyl value, acid esters and the rotary viscosity of measuring the bunching product behind the bunching, if recording the hydroxyl value of bunching product is that 50～60mgKOH/g, acid esters are 0.1～2mgKOH/g, rotary viscosity is 4000～8000mPas under 60 ℃ of conditions, then can confirm to make qualified polyester diol.
(2) synthetic performed polymer, by mass percentage, the above-mentioned polyester diol that makes with 35～45%, 4,4 ' diphenylmethanediisocyanate of 10～15% and 35～50% vinyl acetic monomer are as the raw material of synthetic performed polymer;
Preparation process is as follows:
Make solid content after the vinyl acetic monomer of the above-mentioned polyester diol that makes of 35～45% in the above-mentioned prescription, 4,4 ' diphenylmethanediisocyanate of 10～15% and 35～50% mixed and be 50%～65%, isocyano-content is 3～5% performed polymer;
(3) secondary chain extension, by mass percentage, the above-mentioned performed polymer that makes with 60～70%, 1～5% quadrol and 20～40% vinyl acetic monomer are as the raw material of secondary chain extension step:
The above-mentioned performed polymer that makes of 60～70% in the above-mentioned prescription is dropped in the vinyl acetic monomer of 1～5% quadrol and 20～40%, the dropping time is 0.5～1 hour, make solid content and be 35%～45%, viscosity is the tackiness agent of 4000～7000mPas, is solvent-type polyurethane flocking adhesive.
When Flock Adhesive that present embodiment makes is used, general solidifying agent such as this solvent-type polyurethane flocking adhesive and Baeyer L-75 can be used, mass ratio is 10～20: 1, and the slaking condition is 20～60 ℃ of following constant temperature 6～12 hours.
In the embodiment of the invention by in reasonably combined with crystallinity dibasic alcohol and amorphism diprotic acid of the synthesis phase of preparation polyester diol, and in follow-up secondary chain extension process, introduce an amount of allophanate groups, the molecule segment two ends are with reactive amines group end-blocking, make this solvent-type polyurethane flocking adhesive have excellent body performance, but in operating restraint, has the initial bonding strength height, advantages such as curing speed is fast, its Bearable dry and wet wipe fastness can reach more than 10000 times.The bonding intensity that has overcome existing static flocking tackiness agent existence is relatively poor, the low problem of dried wet rubbing fastness.
Embodiment 2
Present embodiment provides a kind of solvent-type polyurethane flocking adhesive, and this Flock Adhesive specifically comprises for adopting the solvent-type polyurethane flocking adhesive of following method preparation:
(1) preparation polyester diol, according to the form below is got each raw material of preparation polyester diol:
The operation steps of preparation polyester diol is as follows:
(1) esterification:
The dimethyl terephthalate (DMT) of 30 mass parts, 1,4 butyleneglycol of 23 mass parts are joined in the polyester synthesis reactor, be warming up to 210～230 ℃, reacted 3 hours, finish an esterification; Distillating methyl alcohol in the esterification process is 6.80 mass parts;
(2) secondary esterification:
The m-phthalic acid of adding 22 mass parts, 1,6 hexylene glycol of 25 mass parts are warming up to 210～230 ℃ in the reaction system of the polyester synthesis reactor after an above-mentioned esterification, react 5 hours, finish the secondary esterification; In the secondary esterification process, note observing the water outlet situation, keep the aquifer yield of polyester synthesis reactor to be stabilized in per hour for preparing 0.5～1% of the raw materials used total mass of polyester diol; Treat that esterification finishes, the acid number of measuring product is 15mgKOH/g (meeting the requirement of acid number≤20mgKOH/g), shows that esterification is qualified;
(3) polycondensation:
To taking out rough vacuum in the above-mentioned polyester synthesis reactor of finishing after the secondary esterification, vacuum tightness is-0.02Mpa～-0.04Mpa, take out rough vacuum 1.5h after, the vacuum line valve of cutting off the polyester synthesis reactor stops to take out rough vacuum, puts overhead product;
To pumping high vacuum in the polyester synthesis reactor that stops to take out rough vacuum, vacuum tightness from-0.05Mpa～-0.09Mpa, the pumping high vacuum time is 2.5h, the still temperature control of polyester synthesis reactor is at 245 ℃～255 ℃; After pumping high vacuum finishes, the Luoci pump that starts the polyester synthesis reactor vacuumizes growing in the polyester synthesis reactor, vacuum tightness will reach-0.094Mpa, long finding time is about 7 hours, overhead product is about 7.5 mass parts, length vacuumizes the aftercondensated reaction and finishes, and the polycondensation product of polycondensation is polyester diol;
After the polycondensation, the rotary viscosity (under 60 ℃ of conditions) of measuring polycondensation product is that 5200mPas, hydroxyl value are that 52mgKOH/g, acid esters are 0.15mgKOH/g, confirms to make qualified polyester diol;
(2) synthetic performed polymer, according to the form below is got synthetic each used raw material of performed polymer:
The operation steps of synthetic performed polymer is as follows:
After the vinyl acetic monomer of the dimethylene diisocyanate of the above-mentioned polyester diol that makes of 40 mass parts, 15 mass parts and 45 mass parts mixed, make solid content and be 55%, isocyano-content is 3.5% performed polymer;
(3) secondary chain extension, the usefulness in the according to the form below are measured each raw material that secondary chain extension is used:
The operation steps of secondary chain extension is as follows:
The above-mentioned performed polymer that makes of 62 mass parts is dropped in the vinyl acetic monomer of the quadrol of 2 mass parts and 36 mass parts, the dropping time is 1 hour, makes solid content and be 36.1%, viscosity is the tackiness agent of 4900mPas, is solvent-type polyurethane flocking adhesive.
Embodiment 3
Present embodiment provides a kind of solvent-type polyurethane flocking adhesive, and this Flock Adhesive specifically comprises for adopting the solvent-type polyurethane flocking adhesive of following method preparation:
(1) preparation polyester diol, according to the form below is got each raw material of preparation polyester diol:
The operation steps of preparation polyester diol is as follows:
(1) esterification:
The dimethyl terephthalate (DMT) of 25 mass parts, 1,4 butyleneglycol of 30 mass parts are joined in the polyester synthesis reactor, be warming up to 210～230 ℃, reacted 2.5 hours, finish an esterification; Distillate methyl alcohol 5.67 mass parts in the esterification process;
(2) secondary esterification:
Adding is warming up to 210～230 ℃ with the m-phthalic acid of 25 mass parts, 1,6 hexylene glycol of 20 mass parts in the reaction system of the polyester synthesis reactor after an above-mentioned esterification, reacts 5.5 hours, finishes the secondary esterification; In the secondary esterification process, note observing the water outlet situation, it per hour is 0.5～1% of the raw materials used total mass of preparation polyester diol that the aquifer yield of maintenance polyester synthesis reactor is stabilized in, and distillates water 5.42 mass parts; Treat that the secondary esterification finishes, the acid number of measuring product is 16mgKOH/g (meeting the requirement of acid number≤20mgKOH/g), shows that esterification is qualified;
(3) polycondensation:
To taking out rough vacuum in the above-mentioned polyester synthesis reactor of finishing after the secondary esterification, vacuum tightness is-0.02Mpa～-0.04Mpa, take out rough vacuum after 3 hours, the vacuum line valve of cutting off the polyester synthesis reactor stops to take out rough vacuum, puts overhead product;
To pumping high vacuum in the polyester synthesis reactor that stops to take out rough vacuum, high vacuum from-0.05Mpa～-0.09Mpa, the pumping high vacuum time is about 3h, the still temperature control of polyester synthesis reactor is at 245 ℃～255 ℃; After pumping high vacuum finished, the Luoci pump that starts the polyester synthesis reactor was grown and is vacuumized, and vacuum tightness will reach-0.094Mpa, long finding time is about 6.8 hours, overhead product is about 13.2 mass parts, and length vacuumizes the aftercondensated reaction and finishes, and the polycondensation product of polycondensation is polyester diol;
After the polycondensation, surveying polyester A rotary viscosity (under 60 ℃ of conditions) is that 4800mPas, hydroxyl value are that 58mgKOH/g, acid esters are 0.14mgKOH/g, confirms to make qualified polyester diol;
(2) synthetic performed polymer, according to the form below is got synthetic each used raw material of performed polymer:
The operation steps of synthetic performed polymer is as follows:
After the vinyl acetic monomer of 4,4 ' diphenylmethanediisocyanate of the above-mentioned polyester diol that makes of 45 mass parts, 15 mass parts and 40 mass parts mixed, make solid content and be 60%, isocyano-content is 3.1% performed polymer;
(3) secondary chain extension, the usefulness in the according to the form below are measured each raw material that secondary chain extension is used:
The operation steps of secondary chain extension is as follows:
The above-mentioned performed polymer that makes of 70 mass parts is dropped in the vinyl acetic monomer of the quadrol of 3 mass parts and 27 mass parts, the dropping time is 0.6 hour, makes solid content and be 45%, viscosity is the tackiness agent of 6400mPas, is solvent-type polyurethane flocking adhesive.
In sum, in the embodiment of the invention, polyester diol synthesis phase in the preparation method, reasonably combined with crystallinity dibasic alcohol and amorphism diprotic acid, and in follow-up secondary chain extension process, introduce an amount of allophanate groups, make the molecule segment two ends with reactive amines group end-blocking, make the flocking glue of polyurethane that makes have excellent body performance, but have the initial bonding strength height in operating restraint, curing speed is fast, and the Bearable dry and wet wipe fastness can reach more than 10000 times.
The above; only for the preferable embodiment of the present invention, but protection scope of the present invention is not limited thereto, and anyly is familiar with those skilled in the art in the technical scope that the present invention discloses; the variation that can expect easily or replacement all should be encompassed within protection scope of the present invention.Therefore, protection scope of the present invention should be as the criterion with the protection domain of claims.
Claims (7)
1. a solvent-type polyurethane flocking adhesive is characterized in that, this Flock Adhesive is prepared from by following step:
Preparation polyester diol: by mass percentage, dimethyl terephthalate (DMT) with 25～35%, 15～30% 1,4 butyleneglycols, 15～30% m-phthalic acid and 20～30% 1,6 hexylene glycols are raw material, dimethyl terephthalate (DMT) and the mixing of 1,4 butyleneglycol are carried out esterification one time, add m-phthalic acid and 1 after the esterification, 6 hexylene glycols carry out the secondary esterification, and the reaction system after the secondary esterification is carried out making polyester diol after the polycondensation;
Synthetic performed polymer: by mass percentage, the above-mentioned polyester diol that makes with 35～45%, 10～15% 4,4 ' diphenylmethanediisocyanate and 35～50% vinyl acetic monomer are raw material, to make performed polymer after the above-mentioned polyester diol that makes and 4,4 ' diphenylmethanediisocyanate and the vinyl acetic monomer mixing;
Secondary chain extension: by mass percentage, above-mentioned synthetic performed polymer with 60～70%, 1～5% quadrol and 20～40% vinyl acetic monomer are raw material, the above-mentioned performed polymer that makes is dropped in quadrol and the vinyl acetic monomer, make solid content and be 35%～45%, viscosity is the tackiness agent of 4000～7000mPas, is solvent-type polyurethane flocking adhesive.
2. solvent-type polyurethane flocking adhesive as claimed in claim 1 is characterized in that, in the described preparation polyester diol reaction system after the secondary esterification is carried out making polyester diol after the polycondensation and comprises:
Reaction system after the secondary esterification hanged down successively vacuumize, height vacuumizes and grow the polycondensation that vacuumizes after make polyester diol.
3. the preparation method of a solvent-type polyurethane flocking adhesive is characterized in that, comprising:
The preparation polyester diol, used each raw material is all by mass percentage in the step of this preparation polyester diol:
An esterification:
Dimethyl terephthalate (DMT) with 25～35%, 15～30% 1,4 butyleneglycol join and are warming up to 210～230 ℃ in the polyester synthesis reactor, react 2～3 hours, finish an esterification;
The secondary esterification:
Be warming up to 210～230 ℃ after in the reaction system of the above-mentioned polyester synthesis reactor of finishing an esterification, adding 15～30% m-phthalic acid, 20～30% 1,6 hexylene glycol, reacted 5～6 hours, finish the secondary esterification;
Polycondensation:
To taking out rough vacuum in the above-mentioned polyester synthesis reactor of finishing after the secondary esterification, vacuum tightness from-0.02Mpa～-0.04Mpa, take out rough vacuum and stop after 2～3 hours, put overhead product;
To pumping high vacuum in the above-mentioned polyester synthesis reactor of taking out after rough vacuum is finished, vacuum tightness from-0.05Mpa～-0.09Mpa, the pumping high vacuum time is 2.5～3.5 hours, the still temperature control of polyester synthesis reactor is at 245 ℃～255 ℃ in the pumping high vacuum process;
After pumping high vacuum finishes, grow in the polyester synthesis reactor and vacuumize, vacuum tightness will reach-0.094Mpa; The long pumpdown time is 6～8 hours, puts overhead product, and length vacuumizes the aftercondensated reaction and finishes, and the product of polycondensation is polyester diol;
Synthetic performed polymer, used each raw material is all by mass percentage in the step of this synthetic performed polymer:
Make solid content after the polyester diol that above-mentioned preparation polyester diol step with 35～45% makes, 4,4 ' diphenylmethanediisocyanate of 10～15%, 35～50% vinyl acetic monomer mix and be 50%～65%, isocyano-content is 3～5% performed polymer;
Secondary chain extension, used each raw material is all by mass percentage in the step of this secondary chain extension:
The performed polymer that makes in 60～70% the above-mentioned synthetic performed polymer step is dropped in the vinyl acetic monomer of 1～5% quadrol and 20～40%, the dropping time is 0.5～1 hour, make solid content and be 35%～45%, viscosity is the tackiness agent of 4000～7000mPas, is solvent-type polyurethane flocking adhesive.
4. the preparation method of solvent-type polyurethane flocking adhesive as claimed in claim 3, it is characterized in that, an esterif iotacation step of described preparation polyester diol also comprises: after one time esterification finishes, confirm the step that esterification is whether qualified by the acid number of measuring product, if measure product acid number≤20mgKOH/g, confirm that then an esterification is qualified.
5. the preparation method of solvent-type polyurethane flocking adhesive as claimed in claim 3 is characterized in that, in the esterification process of described preparation polyester diol, keeps the alcohol amount to be stabilized in and per hour is 1.5～3% of the raw materials used total mass of preparation polyester diol.
6. the preparation method of solvent-type polyurethane flocking adhesive as claimed in claim 3, it is characterized in that, in the secondary esterification process of described preparation polyester diol, keep the aquifer yield of polyester synthesis reactor to be stabilized in per hour for preparing 2～4% of the raw materials used total mass of polyester diol.
7. the preparation method of solvent-type polyurethane flocking adhesive as claimed in claim 3, it is characterized in that, after the polycondensation steps of described preparation polyester diol is finished, also comprise: determine by hydroxyl value, acid esters and the rotary viscosity of measuring polycondensation product whether polycondensation makes the step of qualified polyester diol, if measuring the hydroxyl value of polycondensation product is that 50～60mgKOH/g, acid esters are that 0.1～2mgKOH/g, the rotary viscosity under 60 ℃ of conditions are 4000～8000mPas, then confirm to make qualified polyester diol.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102250577A (en) * | 2011-05-24 | 2011-11-23 | 北京高盟新材料股份有限公司 | Preparation method of composite adhesive used for solar energy backboard |
| CN109536114A (en) * | 2018-12-03 | 2019-03-29 | 苏州市陆氏新材料有限公司 | A kind of preparation method of the dedicated Antistatic type PU Flock Adhesive of metal |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101633828A (en) * | 2008-07-22 | 2010-01-27 | 北京高盟化工有限公司 | High-temperature resistant waterborne polyurethane adhesive and preparation method thereof |
| CN101701141A (en) * | 2009-08-31 | 2010-05-05 | 北京高盟化工有限公司 | Preparation method of monocomponent moisturecured bonding agent for reflecting material |
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Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101633828A (en) * | 2008-07-22 | 2010-01-27 | 北京高盟化工有限公司 | High-temperature resistant waterborne polyurethane adhesive and preparation method thereof |
| CN101701141A (en) * | 2009-08-31 | 2010-05-05 | 北京高盟化工有限公司 | Preparation method of monocomponent moisturecured bonding agent for reflecting material |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102250577A (en) * | 2011-05-24 | 2011-11-23 | 北京高盟新材料股份有限公司 | Preparation method of composite adhesive used for solar energy backboard |
| CN102250577B (en) * | 2011-05-24 | 2013-07-10 | 南通高盟新材料有限公司 | Preparation method of composite adhesive used for solar energy backboard |
| CN109536114A (en) * | 2018-12-03 | 2019-03-29 | 苏州市陆氏新材料有限公司 | A kind of preparation method of the dedicated Antistatic type PU Flock Adhesive of metal |
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