CN103396753A - Preparation method of hot-melt polyurethane resin for bonding material - Google Patents

Preparation method of hot-melt polyurethane resin for bonding material Download PDF

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CN103396753A
CN103396753A CN2013103554118A CN201310355411A CN103396753A CN 103396753 A CN103396753 A CN 103396753A CN 2013103554118 A CN2013103554118 A CN 2013103554118A CN 201310355411 A CN201310355411 A CN 201310355411A CN 103396753 A CN103396753 A CN 103396753A
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polyurethane resin
preparation
adhesives
hot melt
melt type
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CN103396753B (en
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廖学明
朱天社
朱天寿
唐克卫
张丹年
刘婧
刘建利
刘晓春
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XI'AN GREAT SKY NEW MATERIAL CO Ltd
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XI'AN GREAT SKY NEW MATERIAL CO Ltd
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Abstract

The invention discloses a preparation method of hot-melt polyurethane resin for a bonding material. The preparation method comprises the following steps of performing a dehydration treatment on polyester polyol, polyether polyol, natural oligomer polyol or a mixture of two or more of the polyols aforementioned in certain conditions; adding an amine catalyst or a metal organic compound catalyst, and uniformly stirring and mixing at a room temperature; then reacting the mixture obtained from the former step with polyisocyanate or diisocyanate at 50-70 DEG C; after reacting for a certain time, adding an appropriate amount of a chain extender in the system (an appropriate amount of a good solvent can be added as needed to adjust the viscosity); after the chain extension reaction is concluded, adding a certain amount of acrylate with hydroxyl and a certain amount of an antioxidant in the system; determining the content of NCO via a titration method, when the needed theoretical value is achieved, stopping the reaction, and discharging, thereby obtaining the needed hot-melt polyurethane resin for the bonding material. The hot-melt polyurethane resin for the bonding material is applied to the field of medicine and tobacco packaging as an adhesive, and has the greatest advantages of high bonding strength, low viscosity and low readily oxidizable substance content, and is beneficial to customer use and cost reduction.

Description

A kind of adhesives preparation method of hot melt type polyurethane resin
Technical field
The invention belongs to the sizing agent field, be specifically related to the preparation method of a kind of adhesives with the hot melt type polyurethane resin.
Background technology
All the time, at packaging field, especially the adhesive for polyurethane of medicine and the use of tobacco package field mainly contains solvent borne polyurethane sizing agent, the glutinous agent of two-component polyurethane adhesive and one-component solvent-free type polyurethane sizing agent.The equal Shortcomings of above three class sizing agent is unfavorable for application.Embody a concentrated reflection of that viscosity is bigger than normal is unfavorable for that coating uses; Bonding strength is not high, is embodied in to grow set time to cause initial adhesive strength poor, and is especially not high to the bonding force of PVC sheet material and aluminium foil; Existing solvent borne polyurethane sizing agent system need to be carried out adjusting viscosity with a large amount of organic solvents, although reduced viscosity by the method for adding a large amount of organic solvents, glue spread does not reach requirement, and readily oxidizable substance content has the phenomenon of severe overweight.
Summary of the invention
The object of the present invention is to provide the preparation method of a kind of adhesives with the hot melt type polyurethane resin, it is concentrated and has solved the existing deficiency of existing adhesive for polyurethane: as solvent borne polyurethane sizing agent system consumption of organic solvent, too much cause glue spread on the low side, the one-component solvent-free type polyurethane sizing agent viscosity gluing that is unfavorable for bigger than normal, the problems such as application art complexity of the glutinous agent of two-component polyurethane adhesive; The present invention has also solved above three types adhesive for polyurethane readily oxidizable substance content overproof simultaneously, bonding strength is on the low side, especially initial adhesive strength problem on the low side.
Technical solution of the present invention is:
A kind of adhesives preparation method of hot melt type polyurethane resin, its special character is, comprises the following steps:
1] processed is carried out in two or more mixture of polyester polyol, polyether glycol, natural oligomer polyol or above polyvalent alcohol, all molecular mass is between 1000-5000 relatively for the number of described polyester polyol or polyether glycol, and viscosity is between 800-2000mPa.S (25 ℃);
2] add tertiary amines or Catalyzed by Organometallic Compounds agent, stirring at room mixes;
3] add again polyisocyanates or vulcabond stirring at room 30 minutes, then be warming up to reaction under 50-70 ℃, react after 1-1.5 hour, in system, add chainextender to continue reaction;
4] reaction is after 3-5 hour, and chain extending reaction adds hydroxyl acrylate and oxidation inhibitor to system after finishing again;
5] by volumetry, determine the content of NCO, when reaching required theoretical value, discharging, namely obtain required adhesives hot melt type polyurethane resin.
Above-mentioned steps 3] while adding chainextender, add the good solvent of adjusting viscosity.Effect is better.
By weight, each component proportion is for the starting material of above-mentioned each reaction and auxiliary dosage:
Polyisocyanates or vulcabond: 14-32
Polyester polyol is or/and polyether glycol: 60-80
Acrylate: 4.5-5
Chainextender: 1.5-3
Good solvent 80-200
Catalyzer: 0.5-1
Oxidation inhibitor: 0.5-1.
Above-mentioned processed, that polyester polyol or polyether glycol or the mixture of the two are added in reactor, start stirring, and the heating that heats up, make liquid temperature reach 50-70 ℃ of left and right, start vacuum pump, make vacuum tightness in reactor rise to slowly 0.098-0.1MPa, controlling temperature in the kettle is 3 hours, 110 ℃ of left and right, and discharging, be placed in airtight storage tank standby.
the above-mentioned content that passes through titration measuring NCO is determined level of response, its method is described as: take 3.5~6.5g prepolymer, put into the dry flask of crossing, the Di-n-Butyl Amine solution that adds the new preparation of 20mL with transfer pipet, the THF that adds again the 50mL drying, shake up, add the 100mL anhydrous isopropyl alcohol, with the agent of giving instruction of 0.5mL tetrabromo-mcresolsulfonphthalein, with the hydrochloric acid soln of 1N, be titrated to yellow and be terminal, finally do again blank assay, then by NCO%=mLHCl blank-mLHCl sample/example weight x4.2, calculate the content of NCO group, when reaching theoretical value, NCO content represents that reaction finishes, discharging, obtain required adhesives hot melt type polyurethane resin, described Di-n-Butyl Amine solution is to the 1000mL preparation, to obtain with dry dilution with toluene by 338mL Di-n-Butyl Amine in volumetric flask.
Above-mentioned polyisocyanates or vulcabond comprise vulcabond, triisocyanate and polyisocyanates, and described vulcabond comprises any of TDI, MDI, HDI, TMHDI, IPDI and HXDI combination.Especially better with one or both compound use effects wherein.
Above-mentioned polyether glycol and polyester polyol comprise any of PDA, PEA, PBA, PCL, PCDL, PTMEG, PEG and PPG combination; Described natural polyvalent alcohol comprises vegetable oil polyol and rosin ester polyvalent alcohol.Especially with PCL or PCL, with two kinds of PTMEG, mix result of use the best.
Above-mentioned hydroxy acrylate comprises Hydroxyethyl acrylate, Propylene glycol monoacrylate, hydroxyethyl methylacrylate, Rocryl 410, pentaerythritol triacrylate, Dipentaerythritol five acrylate and epoxy acrylate.The present invention selects epoxy acrylate or (methyl) Propylene glycol monoacrylate as the function monomer end-blocking.
Above-mentioned chainextender comprises BDO, ethylene glycol, 1,2-PD, 1,3-PD, glycol ether, 1,6-hexylene glycol, MOCA, DMTDA, DETDA, thanomin, diethanolamine or trolamine;
Described good solvent comprises N-Methyl pyrrolidone (NMP), DMF (DMF) ' acetone, pimelinketone, N-BUTYL ACETATE;
Described catalyzer comprises triethylenediamine, two (dimethylaminoethyl) ether, 2-(2-dimethylamino-oxyethyl group) ethanol, stannous octoate, dibutyl tin laurate, carboxylic acid potassium, organic mercury and organic lead.Especially using a kind of as optimal selection in stannous octoate, dibutyl tin laurate.
Described oxidation inhibitor comprises any of 2,6 ditertiary butyl p cresol, four [β-(3,5-di-tert-butyl-hydroxy phenyl) propionic acid] pentaerythritol ester, butyl or octyl group aniline and phosphorous acid ester combination.Select wherein a kind of or have better effect with the phosphorous acid ester compound use.
A kind of adhesives that utilizes above-mentioned preparation method to prepare hot melt type polyurethane resin, its special being: this adhesives is equipped with appropriate organic solvent with the hot melt type polyurethane resin and is applied to medicine and tobacco package as sizing agent.
A kind of adhesives of the present invention preparation method of hot melt type polyurethane resin, wherein polyvalent alcohol is after processed, added organotin or tertiary amine catalyst and polyisocyanates stirring at room 30 minutes, heat up again and react the regular hour between 50-70 ℃, then add chainextender to carry out chain extending reaction, total reaction time is at 3-5 hour.
A kind of adhesives of the present invention, with the preparation method of hot melt type polyurethane resin, wherein, adds epoxy acrylate or (methyl) Propylene glycol monoacrylate to carry out end capping, 50-70 ℃ of reaction times at 3-7 hour.
Advantage of the present invention is mainly reflected in:
Its product of the present invention is colourless transparent liquid, is equipped with a small amount of organic solvent and namely obtains the low-viscosity polyurethane sizing agent, and convenient coating is used.
It is mixed with the low-viscosity polyurethane sizing agent the present invention, and bonding strength comprises that initial adhesive strength is all far above existing various types of adhesive for polyurethane.
It is mixed with the low-viscosity polyurethane sizing agent the present invention, and readily oxidizable substance content is 0 or levels off to 0 after measured.
It is mixed with adhesive for polyurethane the present invention, and outstanding feature is that viscosity is low and solid content is high, and glue spread can reach national and foreign standards.
The present invention only need to add a small amount of organic solvent or good solvent and namely obtain adhesive for polyurethane, and principal feature is that viscosity is low, readily oxidizable substance content is low, solid content is high, bonding strength is high and glue spread is high.
The present invention only need to add a small amount of organic solvent or good solvent and namely obtain adhesive for polyurethane, for the packing of drug packages or other field provides practicable solution, is particularly useful for bonding between PVC sheet material and aluminium foil or other section bars.
Embodiment
For further illustrating the technology of the present invention, below in conjunction with specific embodiment, be described in detail, the present invention includes but be not limited to following examples.
Embodiment 1
A kind of adhesives preparation method of hot melt type polyurethane resin, wherein, each component concentration is by mass parts: TDI:HDI:PTMEG:PEG:DBO: epoxy acrylate: organotin: oxidation inhibitor: good solvent is 10:4:60:20:1.5:4.5:0.5:0.5:100.
A kind of adhesives preparation method of hot melt type polyurethane resin, its preparation process is as follows: PTMEG and PEG are carried out to processed under certain condition, add organotin catalysts, stirring at room mixes, add respectively again TDI and HDI, be warming up between 50-70 ℃, after the reaction certain hour, in system, add the DBO(of aforementioned proportion can add as required appropriate good solvent adjusting viscosity), above two-step reaction total time is no more than 5 hours, then adds the oxidation inhibitor insulation reaction of epoxy acrylate and specified amount.By volumetry, determine the content of NCO, when reaching required theoretical value, stopped reaction, discharging, namely obtain required urethane resin.
Wherein, the number of PTMEG and PEG when all relative molecular mass is 1000,25 ℃ viscosity in the 600mPa.S left and right.
Wherein, PTMEG and PEG needed through processed before adding TDI and MDI, be after PTMEG and PEG drop into reactor, heat up, when the temperature of mixture reaches 50 ℃, start vacuum pump, make vacuum tightness in reactor rise to slowly 0.098-0.1MPa, control temperature in the kettle and be 3 hours, 110 ℃ of left and right, standby.
wherein said content by titration measuring NCO is determined level of response, its method is described as: take the 5g prepolymer, put into the dry flask of crossing, the 20mL Di-n-Butyl Amine solution that adds new preparation with transfer pipet, the THF that adds again the 50mL drying, shake up, add the 100mL anhydrous isopropyl alcohol, with the agent of giving instruction of 0.5mL tetrabromo-mcresolsulfonphthalein, with the hydrochloric acid soln of 1N, be titrated to yellow and be terminal, finally do again blank assay, then by NCO%=mLHCl blank-mLHCl sample/example weight x4.2, calculate the content of NCO group, when reaching theoretical value, NCO content represents that reaction finishes, discharging, obtain required adhesives hot melt type polyurethane resin.
product of the present invention only need to add a small amount of organic solvent or good solvent and namely obtain adhesive for polyurethane, principal feature is that viscosity is low, readily oxidizable substance content is low, solid content is high, bonding strength is high and glue spread is high, product viscosity of the present invention was less than 50 seconds (at present existing this type of product be generally 60-80 second), readily oxidizable substance Han Liang<=0.5(existing this type of product at present is generally 1 left and right), solid content 25%(existing this type of product at present is generally 20% left and right), bonding strength 11-13N(existing this type of product at present is 8-10N), for drug packages or other need the packaging field of high-solid lower-viscosity sizing agent that practicable solution is provided, be particularly useful for bonding between PVC sheet material and aluminium foil or other section bars.
Embodiment 2
A kind of adhesives is with the preparation method of hot melt type polyurethane resin, and wherein, each component concentration is by mass parts: IPDI:MDI:PTMEG:PCL:DBO: epoxy acrylate: tertiary amine: oxidation inhibitor: good solvent is 12:20:30:30:3:5:0.5:0.5:80.
A kind of adhesives preparation method of hot melt type polyurethane resin, its preparation process is as follows: PTMEG and PCL are carried out to processed under certain condition, add tertiary amine catalyst, stirring at room mixes, add respectively again IPDI and MDI, be warming up between 50-70 ℃, after the reaction certain hour, in system, add the DBO(of aforementioned proportion can add as required appropriate good solvent adjusting viscosity), above two-step reaction total time is no more than 5 hours, then adds the oxidation inhibitor insulation reaction of epoxy acrylate and specified amount.By volumetry, determine the content of NCO, when reaching required theoretical value, stopped reaction, discharging, namely obtain required adhesives hot melt type polyurethane resin.
Wherein, the number of PTMEG and PEG when all relative molecular mass is 1000,25 ℃ viscosity in the 600mPa.S left and right.
Wherein, PTMEG and PEG needed through processed before adding TDI and MDI, be after PTMEG and PEG drop into reactor, heat up, when the temperature of mixture reaches 50 ℃, start vacuum pump, make vacuum tightness in reactor rise to slowly 0.098-0.1MPa, control temperature in the kettle and be 3 hours, 110 ℃ of left and right, standby.
wherein said content by titration measuring NCO is determined level of response, its method is described as: take the 5g prepolymer, put into the dry flask of crossing, the 20mL Di-n-Butyl Amine solution that adds new preparation with transfer pipet, the THF that adds again the 50mL drying, shake up, add the 100mL anhydrous isopropyl alcohol, with the agent of giving instruction of 0.5mL tetrabromo-mcresolsulfonphthalein, with the hydrochloric acid soln of 1N, be titrated to yellow and be terminal, finally do again blank assay, then by NCO%=mLHCl blank-mLHCl sample/example weight x4.2, calculate the content of NCO group, when reaching theoretical value, NCO content represents that reaction finishes, discharging, obtain required urethane resin.
product of the present invention only need to add a small amount of organic solvent or good solvent and namely obtain adhesive for polyurethane, principal feature is that viscosity is low, readily oxidizable substance content is low, solid content is high, bonding strength is high and glue spread is high, product viscosity of the present invention was less than 50 seconds (at present existing this type of product be generally 60-80 second), readily oxidizable substance Han Liang<=0.5(existing this type of product at present is generally 1 left and right), solid content 25%(existing this type of product at present is generally 20% left and right), bonding strength 11-13N(existing this type of product at present is 8-10N), for drug packages or other need the packaging field of high-solid lower-viscosity sizing agent that practicable solution is provided, be particularly useful for bonding between PVC sheet material and aluminium foil or other section bars.
Embodiment 3
A kind of adhesives preparation method of hot melt type polyurethane resin, wherein, each component concentration is by mass parts: IPDI:MDI:HDI:PTMEG:PCL:PPG: ethylene glycol: epoxy acrylate: organotin: Resorcinol: good solvent is 8:8:16:20:20:20:3:5:0.5:1:200.
A kind of adhesives preparation method of hot melt type polyurethane resin, its preparation process is as follows: PTMEG, PCL and PPG are carried out to processed under certain condition, add organotin catalysts, stirring at room mixes, add respectively again IPDI, HDI and MDI, be warming up between 50-70 ℃, after the reaction certain hour, in system, add the DBO(of aforementioned proportion can add as required appropriate good solvent adjusting viscosity), above two-step reaction total time is no more than 5 hours, then adds the oxidation inhibitor insulation reaction of epoxy acrylate and specified amount.By volumetry, determine the content of NCO, when reaching required theoretical value, stopped reaction, discharging, namely obtain required urethane resin.
Wherein, the number of PTMEG, PPG and PEG when all relative molecular mass is 1000,25 ℃ viscosity in the 600mPa.S left and right.
Wherein, vulcabond needed through processed before adding oligopolymer dibasic alcohol system, be after the oligopolymer dibasic alcohol drops into reactor, heat up, when the temperature of mixture reaches 50 ℃, start vacuum pump, make vacuum tightness in reactor rise to slowly 0.098-0.1MPa, control temperature in the kettle and be 3 hours, 110 ℃ of left and right, standby.
wherein said content by titration measuring NCO is determined level of response, its method is described as: take the 5g prepolymer, put into the dry flask of crossing, the 20mL Di-n-Butyl Amine solution that adds new preparation with transfer pipet, the THF that adds again the 50mL drying, shake up, add the 100mL anhydrous isopropyl alcohol, with the agent of giving instruction of 0.5mL tetrabromo-mcresolsulfonphthalein, with the hydrochloric acid soln of 1N, be titrated to yellow and be terminal, finally do again blank assay, then by NCO%=mLHCl blank-mLHCl sample/example weight x4.2, calculate the content of NCO group, when reaching theoretical value, NCO content represents that reaction finishes, discharging, obtain required adhesives hot melt type polyurethane resin.
product of the present invention only need to add a small amount of organic solvent or good solvent and namely obtain adhesive for polyurethane, principal feature is that viscosity is low, readily oxidizable substance content is low, solid content is high, bonding strength is high and glue spread is high, product viscosity of the present invention was less than 50 seconds (at present existing this type of product be generally 60-80 second), readily oxidizable substance Han Liang<=0.5(existing this type of product at present is generally 1 left and right), solid content 25%(existing this type of product at present is generally 20% left and right), bonding strength 11-13N(existing this type of product at present is 8-10N), for drug packages or other need the packaging field of high-solid lower-viscosity sizing agent that practicable solution is provided, be particularly useful for bonding between PVC sheet material and aluminium foil or other section bars.
Embodiment 4
A kind of adhesives preparation method of hot melt type polyurethane resin, wherein, each component concentration is by mass parts: the IPDI:HDI:PTMEG:PCL:PPG:DBO:(methyl) Propylene glycol monoacrylate: organotin: Resorcinol: good solvent is 7:7:16:20:40:20:1.5:4.5:0.5:1:120.
A kind of adhesives preparation method of hot melt type polyurethane resin, its preparation process is as follows: PTMEG, PCL and PPG are carried out to processed under certain condition, add organotin catalysts, stirring at room mixes, then adds respectively IPDI and HDI, be warming up between 50-70 ℃, after the reaction certain hour, to the 1,3 butylene glycol that adds aforementioned proportion in system, above two-step reaction total time is no more than 5 hours, then adds the oxidation inhibitor insulation reaction of epoxy acrylate and specified amount.By volumetry, determine the content of NCO, when reaching required theoretical value, stopped reaction, discharging, namely obtain required adhesives hot melt type polyurethane resin.
Wherein, the number of PTMEG, PPG and PEG when all relative molecular mass is 1000,25 ℃ viscosity in the 600mPa.S left and right.
Wherein, vulcabond needed through processed before adding oligopolymer dibasic alcohol system, be after the oligopolymer dibasic alcohol drops into reactor, heat up, when the temperature of mixture reaches 50 ℃, start vacuum pump, make vacuum tightness in reactor rise to slowly 0.098-0.1MPa, control temperature in the kettle and be 3 hours, 110 ℃ of left and right, standby.
wherein said content by titration measuring NCO is determined level of response, its method is described as: take the 5g prepolymer, put into the dry flask of crossing, the 20mL Di-n-Butyl Amine solution that adds new preparation with transfer pipet, the THF that adds again the 50mL drying, shake up, add the 100mL anhydrous isopropyl alcohol, with the agent of giving instruction of 0.5mL tetrabromo-mcresolsulfonphthalein, with the hydrochloric acid soln of 1N, be titrated to yellow and be terminal, finally do again blank assay, then by NCO%=mLHCl blank-mLHCl sample/example weight x4.2, calculate the content of NCO group, when reaching theoretical value, NCO content represents that reaction finishes, discharging, obtain required urethane resin.
product of the present invention only need to add a small amount of organic solvent or good solvent and namely obtain adhesive for polyurethane, principal feature is that viscosity is low, readily oxidizable substance content is low, solid content is high, bonding strength is high and glue spread is high, product viscosity of the present invention was less than 50 seconds (at present existing this type of product be generally 60-80 second), readily oxidizable substance Han Liang<=0.5(existing this type of product at present is generally 1 left and right), solid content 25%(existing this type of product at present is generally 20% left and right), bonding strength 11-13N(existing this type of product at present is 8-10N), for drug packages or other need the packaging field of high-solid lower-viscosity sizing agent that practicable solution is provided, be particularly useful for bonding between PVC sheet material and aluminium foil or other section bars.
Embodiment 5
A kind of adhesives preparation method of hot melt type polyurethane resin, wherein, each component concentration is by mass parts: IPDI:HDI:PTMEG:PCL:PPG:1, and 3-butyleneglycol: bisphenol A epoxy acrylate: organotin: Resorcinol: good solvent is 7:7:16:20:40:20:1.5:4.5:0.5:1:80.
A kind of adhesives preparation method of hot melt type polyurethane resin, its preparation process is as follows: PTMEG, PCL and PPG are carried out to processed under certain condition, add organotin catalysts, stirring at room mixes, then adds respectively IPDI and HDI, be warming up between 50-70 ℃, after the reaction certain hour, to the 1,3 butylene glycol that adds aforementioned proportion in system, above two-step reaction total time is no more than 5 hours, then adds the oxidation inhibitor insulation reaction of epoxy acrylate and specified amount.By volumetry, determine the content of NCO, when reaching required theoretical value, stopped reaction, discharging, namely obtain required adhesives hot melt type polyurethane resin.
Wherein, the number of PTMEG, PPG and PEG when all relative molecular mass is 1000,25 ℃ viscosity in the 600mPa.S left and right.
Wherein, vulcabond needed through processed before adding oligopolymer dibasic alcohol system, be after the oligopolymer dibasic alcohol drops into reactor, heat up, when the temperature of mixture reaches 50 ℃, start vacuum pump, make vacuum tightness in reactor rise to slowly 0.098-0.1MPa, control temperature in the kettle and be 3 hours, 110 ℃ of left and right, standby.
wherein said content by titration measuring NCO is determined level of response, its method is described as: take the 5g prepolymer, put into the dry flask of crossing, the 20mL Di-n-Butyl Amine solution that adds new preparation with transfer pipet, the THF that adds again the 50mL drying, shake up, add the 100mL anhydrous isopropyl alcohol, with the agent of giving instruction of 0.5mL tetrabromo-mcresolsulfonphthalein, with the hydrochloric acid soln of 1N, be titrated to yellow and be terminal, finally do again blank assay, then by NCO%=mLHCl blank-mLHCl sample/example weight x4.2, calculate the content of NCO group, when reaching theoretical value, NCO content represents that reaction finishes, discharging, obtain required urethane resin.
product of the present invention only need to add a small amount of organic solvent or good solvent and namely obtain adhesive for polyurethane, principal feature is that viscosity is low, readily oxidizable substance content is low, solid content is high, bonding strength is high and glue spread is high, product viscosity of the present invention was less than 50 seconds (at present existing this type of product be generally 60-80 second), readily oxidizable substance Han Liang<=0.5(existing this type of product at present is generally 1 left and right), solid content 25%(existing this type of product at present is generally 20% left and right), bonding strength 11-13N(existing this type of product at present is 8-10N), for drug packages or other need the packaging field of high-solid lower-viscosity sizing agent that practicable solution is provided, be particularly useful for bonding between PVC sheet material and aluminium foil or other section bars.

Claims (10)

1. the preparation method of an adhesives use hot melt type polyurethane resin, is characterized in that, comprises the following steps:
1] processed is carried out in two or more mixture of polyester polyol, polyether glycol, natural oligomer polyol or above polyvalent alcohol, all molecular mass is between 1000-5000 relatively for the number of described polyester polyol or polyether glycol, and viscosity is between 800-2000mPa.S (25 ℃);
2] add tertiary amines or Catalyzed by Organometallic Compounds agent, stirring at room mixes;
3] add again polyisocyanates or vulcabond stirring at room 30 minutes, then be warming up to reaction under 50-70 ℃, react after 1-1.5 hour, in system, add chainextender to continue reaction;
4] reaction is after 3-5 hour, and chain extending reaction adds hydroxyl acrylate and oxidation inhibitor to system after finishing again;
5] by volumetry, determine the content of NCO, when reaching required theoretical value, discharging, namely obtain required adhesives hot melt type polyurethane resin.
2. adhesives, with the preparation method of hot melt type polyurethane resin, is characterized in that: described step 3 according to claim 1] while adding chainextender, also add the good solvent of adjusting viscosity.
3. described adhesives is with the preparation method of hot melt type polyurethane resin according to claim 1 and 2, and it is characterized in that: by weight, each component proportion is for the starting material of described each reaction and auxiliary dosage:
Polyisocyanates or vulcabond: 14-32
Polyester polyol is or/and polyether glycol: 60-80
Acrylate: 4.5-5
Chainextender: 1.5-3
Good solvent 80-200
Catalyzer: 0.5-1
Oxidation inhibitor: 0.5-1.
According to claim 3 adhesives with the preparation method of hot melt type polyurethane resin, it is characterized in that: described processed, be that polyester polyol or polyether glycol or the mixture of the two are added in reactor, start stirring, and the heating that heats up, make liquid temperature reach 50-70 ℃ of left and right, start vacuum pump, make vacuum tightness in reactor rise to slowly 0.098-0.1MPa, controlling temperature in the kettle is 3 hours, 110 ℃ of left and right, discharging, be placed in airtight storage tank standby.
as claimed in claim 4 adhesives with the preparation method of hot melt type polyurethane resin, it is characterized in that: described content by titration measuring NCO is determined level of response, its method is described as: take 3.5~6.5g prepolymer, put into the dry flask of crossing, the Di-n-Butyl Amine solution that adds the new preparation of 20mL with transfer pipet, the THF that adds again the 50mL drying, shake up, add the 100mL anhydrous isopropyl alcohol, with the agent of giving instruction of 0.5mL tetrabromo-mcresolsulfonphthalein, with the hydrochloric acid soln of 1N, be titrated to yellow and be terminal, finally do again blank assay, then by NCO%=mLHCl blank-mLHCl sample/example weight x4.2, calculate the content of NCO group, when reaching theoretical value, NCO content represents that reaction finishes, discharging, obtain required adhesives hot melt type polyurethane resin, described Di-n-Butyl Amine solution is to the 1000mL preparation, to obtain with dry dilution with toluene by 338mL Di-n-Butyl Amine in volumetric flask.
6. adhesives is with the preparation method of hot melt type polyurethane resin according to claim 5, and it is characterized in that: described polyisocyanates or vulcabond comprise vulcabond, triisocyanate and polyisocyanates; Described vulcabond comprises any of TDI, MDI, HDI, TMHDI, IPDI and HXDI combination.
7. adhesives with the preparation method of hot melt type polyurethane resin, is characterized in that according to claim 6:
Described polyether glycol and polyester polyol comprise any of PDA, PEA, PBA, PCL, PCDL, PTMEG, PEG and PPG combination;
Described natural oligomer polyol comprises vegetable oil polyol and rosin ester polyvalent alcohol.
8. adhesives is with the preparation method of hot melt type polyurethane resin according to claim 7, and it is characterized in that: described hydroxy acrylate comprises Hydroxyethyl acrylate, Propylene glycol monoacrylate, hydroxyethyl methylacrylate, Rocryl 410, pentaerythritol triacrylate, Dipentaerythritol five acrylate and epoxy acrylate.
9. adhesives with the preparation method of hot melt type polyurethane resin, is characterized in that according to claim 8:
Described chainextender comprises BDO, ethylene glycol, 1,2-PD, 1,3-PD, glycol ether, 1,6-hexylene glycol, MOCA, DMTDA, DETDA, thanomin, diethanolamine or trolamine;
Described good solvent comprises N-Methyl pyrrolidone (NMP), DMF (DMF) ' acetone, pimelinketone, N-BUTYL ACETATE;
Described catalyzer comprises triethylenediamine, two (dimethylaminoethyl) ether, 2-(2-dimethylamino-oxyethyl group) ethanol, stannous octoate, dibutyl tin laurate, carboxylic acid potassium, organic mercury and organic lead;
Described oxidation inhibitor comprises any of 2,6 ditertiary butyl p cresol, four [β-(3,5-di-tert-butyl-hydroxy phenyl) propionic acid] pentaerythritol ester, butyl or octyl group aniline and phosphorous acid ester combination.
10. the adhesives that utilizes claim 1 preparation method to prepare hot melt type polyurethane resin, it is characterized in that: this adhesives is equipped with appropriate organic solvent with the hot melt type polyurethane resin and is applied to medicine and tobacco package as sizing agent.
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CN103770261B (en) * 2014-01-24 2016-08-31 致恒(天津)实业有限公司 A kind of polyurethane and the bonding process of metal
CN103770261A (en) * 2014-01-24 2014-05-07 致恒(天津)实业有限公司 Polyurethane and metal binding technology
CN104327786A (en) * 2014-11-06 2015-02-04 苏州佰格斯电子科技有限公司 Shrink-proof polyurethane sealant
CN104356631A (en) * 2014-11-06 2015-02-18 苏州佰格斯电子科技有限公司 Durable polyurethane sealant
CN104356633A (en) * 2014-11-06 2015-02-18 苏州佰格斯电子科技有限公司 High-performance polyurethane sealant
CN104927742B (en) * 2015-06-23 2017-05-17 上海东和胶粘剂有限公司 Polyurethane wood structure glue and preparation method thereof
CN104927742A (en) * 2015-06-23 2015-09-23 上海东和胶粘剂有限公司 Polyurethane wood structure glue and preparation method thereof
CN104927745A (en) * 2015-06-24 2015-09-23 杭州星华反光材料有限公司 Adhesive for reflecting elastic fabrics and preparing method thereof
CN105622857A (en) * 2016-04-01 2016-06-01 武汉大学 Preparation method of interpenetrating-network-structure water-based polyurethane nano composite material
CN107384293A (en) * 2017-06-28 2017-11-24 苏州奥斯汀新材料科技有限公司 A kind of preparation method of thermoplastic polyurethane hot melt adhesive
CN108624278A (en) * 2018-05-02 2018-10-09 广东多正树脂科技有限公司 A kind of modified polyurethane cladding glue and preparation method thereof of the room temperature without triphen
CN110600667A (en) * 2019-09-02 2019-12-20 厦门纬达科技有限公司 Thermal composite molding process for pole lug of power lithium battery
CN111979597A (en) * 2020-09-02 2020-11-24 浙江吉仑高分子材料股份有限公司 Method for preparing thermal fuse
CN111979597B (en) * 2020-09-02 2023-06-23 吴键儒 Method for preparing thermal fuse
CN113308207A (en) * 2021-05-31 2021-08-27 东莞市雄林新材料科技股份有限公司 Water-splashing-preventing TPU hot melt adhesive film and preparation method thereof
CN113462347A (en) * 2021-06-04 2021-10-01 武汉海翎化学工业有限公司 Thermosetting solvent-free polyurethane adhesive and preparation method thereof
CN114907812A (en) * 2022-06-21 2022-08-16 武汉弘毅共聚新材料科技有限公司 Low-viscosity VC adhesive for drug encapsulation and preparation method and application thereof
CN114907812B (en) * 2022-06-21 2024-01-30 武汉弘毅共聚新材料科技有限公司 Low-viscosity VC glue for medicine packaging and preparation method and application thereof
CN115093822A (en) * 2022-07-18 2022-09-23 广州市嘉雁粘合剂有限公司 Hot melt adhesive for laminating household appliance panels and preparation method thereof

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