CN102703016A - Preparation method for polyurethane adhesive for binding high-grade books - Google Patents
Preparation method for polyurethane adhesive for binding high-grade books Download PDFInfo
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- CN102703016A CN102703016A CN2012101817398A CN201210181739A CN102703016A CN 102703016 A CN102703016 A CN 102703016A CN 2012101817398 A CN2012101817398 A CN 2012101817398A CN 201210181739 A CN201210181739 A CN 201210181739A CN 102703016 A CN102703016 A CN 102703016A
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Abstract
The invention discloses a preparation method for a polyurethane adhesive for binding high-grade books and belongs to the field of polyurethane adhesive compounding. The steps are as follows: (1) prepolymerization reaction: using hydroxy monomers and isocyanate monomers as main raw materials, and compounding to get prepolymers blocked with OH and NCO respectively; and (2) cross-linking reaction: mixing the two kinds of prepolymers by a certain proportion, and curing to obtain a transparent or semitransparent, flexible and properly hard coating. The invention adopts the two-step compounding method of prepolymerization and cross-linking to compound out a solvent-free double-component polyurethane adhesive; the production process is simple and clean and conforms to the requirement of environmental protection; and the viscosity and the molecular weight of Components A and B can be adjusted through prepolymerization so as to increase bonding strength; the adhesive can be cured in the cross-linking process so as to further improve the bonding strength. (3) The components A and B are liquid at normal temperature, and the viscosity and the curing speed are adjustable; the curing reaction is conducted at room temperature, the operation is convenient, the energy consumption is low, and product storage is stable.
Description
Technical field
The invention belongs to the synthetic field of polyurethane adhesive, relate in particular to the preparation method of a kind of high-grade bookbinding with polyurethane adhesive.
Background technology
In recent years, people improve the requirement of bookbinding quality day by day, mainly concentrate on relatively than bookbinding field behind the seal that falls behind.The bookbinding mode mainly contains traditional thread bindingly to be ordered, binds to order with mucilage binding and order three kinds, and wherein to order be the method that generally adopts to glue, and tackiness agent then is the important supplementary material that glue is ordered.It is numerous that bookbinding sticks with glue the kind of agent, mainly contains starch paste glue (starch paste, Hu dextrin), gelatin (gelatine), PVA (PVAC) emulsion sizing agent, plastic of poly vinyl acetate (EVA) hot melt adhesive, moisture curing reaction type polyurethane (PUR) hot melt adhesive etc.
The gluing relay of starch paste is stronger, but is prone to the moisture absorption deliquescence, and the modulation process temperature influence is very big, and application is restricted; The gelatin water cut is low, rate of drying is fast, can be used for making hard-cover book case etc., but limited because of its source, is synthesized glue gradually and replaces; The PVAC emulsion adhesive, cured glue film water white transparency, but water tolerance, temperature tolerance are poor, and have anti-plasticity, thermo-labile; The EVA hot melt adhesive is the maximum bookbinding material of domestic use, and its bonding strength is high, and curing speed is fast; Flexible, nontoxic, but its in use spread is big, it is perishable to meet solvent; Temperature tolerance is poor, and the books property divided is poor, at adhesive bookbinding during particularly at high-grade books or thicker bookbinding; Be prone to form groove or close suddenly, can produce many troubles, thereby limit its application in high-grade bookbinding field; The bonding property of PUR hot melt adhesive is strong, the heat resistanceheat resistant winter resistance is good, anti-solvent, and the books property divided is good, but it is the performed polymer that has active terminal group, and production, transportation equipment are required height, cost increases.
Solvent-free dual-component polyurethane adhesive is to adopt mass polymerization synthetic tackiness agent; Do not contain any solvent in the system, environmental protection, this series products is made up of first (host), second (solidifying agent) two components; Separately pack; Solved the problem of product need nitrogen protection in one-component polyurethane adhesive preparation, the transportation on the one hand, reduced cost, and effectively improved package stability; On the other hand; Solvent-free dual-component polyurethane adhesive has performance adjustability, wide, the final bond strength of bonding scope than advantages such as single-component adhesive are big; But sticking with glue agent with other bookbindings compares; The set time of solvent-free dual-component polyurethane adhesive is generally longer, and therefore the existing automatic production line of incompatibility is not applied to the bookbinding field at present.
CN102181259A has reported that adhesive bookbinding is with PUR hot melt adhesive and preparation method thereof.With polyester polyol, hexamethylene diisocyanate, diphenylmethanediisocyanate, additive is main raw material, under vacuum condition, carries out prepolymerization reaction; Add the chainextender chain extension after pre-polymerization is accomplished, under feeding nitrogen protection condition, pour out product, pack.This series products bonding strength is high, consumption is few, and has solvent resistance, resistant of high or low temperature and oil resistant China ink aggressiveness, can satisfy the bonding requirements of different paper.But polyurethane hot melt is the performed polymer that has active terminal group, in production, transportation, wants strict secluding air, and is high to equipment requirements, thereby cost significantly increases.
Li Peijin etc. are in " adhesive bookbinding is with the development of EVA hot melt adhesive " literary composition; Reported that with the EVA resin be base resin; Cooperation through tackifier, toughner, viscosity modifier, filler, oxidation inhibitor; Development obtains the adhesive bookbinding hot melt adhesive special, and EVA resin and consumption thereof that the different trades mark have been discussed in the literary composition are to the hot melt adhesive Effect on Performance.Yet the books property divided of using the bookbinding of EVA hot melt adhesive is poor, the shelf time short (about 2-3); And its bookbinding effect is influenced by coating and the printing ink etc. of Substance, use; Limited its application, and comprehensive cost is higher than polyurethane tackifier in high-grade bookbinding field.
CN101903433A has introduced a kind of two-component polyurethane adhesive that is used for binder fibre film product; Comprise two components of polyvalent alcohol component and crosslinked component; Wherein the polyvalent alcohol component is made up of polyester diol, 3-to 14-official ability polyvalent alcohol, hydrophobicity polyvalent alcohol and additional additives or auxiliary, and crosslinked component is made by POLYMETHYLENE POLYPHENYLISOCYANATE.This tackiness agent shows excellent bonding strength, is used for bonding metal, plastics or foam substrate or fibre composite, the base material that can bondingly have a uneven surface with can be with strong adhesive power bridge joint crack or space, T behind the adhesive solidification
gBe higher than 50 ℃, show high physical strength and rigidity.But because its second-order transition temperature is high, rigidity is big, and poor in flexibility is not suitable for the bookbinding field.
Summary of the invention
The present invention has introduced a kind of preparation method of solvent-free dual-component polyurethane adhesive, and is applied in the high-grade bookbinding field.
Operational path of the present invention mainly comprised for two steps: (1) prepolymerization reaction: with carboxylic monomer, isocyanate-monomer is main raw material, synthetic respectively with the OH end-blocking with the end capped performed polymer of NCO; (2) crosslinking reaction: two kinds of performed polymers are mixed by a certain percentage, through solidify makes transparent or semitransparent, snappiness is better, and has the glued membrane of suitable hardness.
High-grade bookbinding of the present invention carries out according to following step with the preparation method of polyurethane adhesive:
(1) prepolymer reaction: with the carboxylic monomer A 1h that under 85 ~ 100 ℃, 0.08 ~ 0.1Mpa vacuum tightness, dewaters, regulate pre-polymerization temperature to 65～90 ℃, add the isocyanate-monomer B and the catalyzer of metering, reaction 2 ~ 3h, synthetic first component; The carboxylic monomer D and the catalyzer that in isocyanate-monomer C, add metering, adjusting pre-polymerization temperature to 70～90 ℃, reaction 2 ~ 3h, synthetic component B;
(2) crosslinking reaction: the first step synthetic first, component B under room temperature (25 ℃), is mixed stirring by certain R value (being isocyano and the mol ratio of hydroxyl), and wherein theoretical R value is 0.9 ~ 1.50.Can obtain high-grade bookbinding and use polyurethane adhesive.
Wherein the carboxylic monomer A in the first component described in the step (1) is polyether polyol, polyester polyol, Viscotrol C, USP Kosher, polyester polyethers polyol blend or polyester Viscotrol C polyol blend, polyethers Viscotrol C polyol blend etc.; Be preferable over and gather hexanodioic acid ethanol ester, polyneopentyl glycol adipate, trihydroxy-polyoxytrimethylene ether, USP Kosher, Viscotrol C, polyoxypropyleneglycol, gather hexanodioic acid-1,4-butanediol ester glycol (PBA); The more preferably mixture of one or more in trihydroxy-polyoxytrimethylene ether, USP Kosher, Viscotrol C, polyethylene glycol adipate, total carboxylic monomer amount accounts for 80～100% of total solids quality.
Wherein the isocyanate-monomer B in the first component described in the step (1) is a tolylene diisocyanate (TDI), 4; 4 ＇-diphenylmethanediisocyanate (MDI), poly methylene poly phenyl poly isocyanate (PAPI), isophorone diisocyanate (IPDI), hexamethylene diisocyanate (HDI); Be preferable over tolylene diisocyanate (TDI), isophorone diisocyanate (IPDI), 4; 4 ＇-diphenylmethanediisocyanate (MDI), its total isocyanate-monomer amount accounts for 0～20% of total solids quality.
Wherein the carboxylic monomer D in the component B described in the step (1) is polyether polyol, polyester polyol, Viscotrol C, USP Kosher, polyester polyethers polyol blend or polyester Viscotrol C polyol blend, polyethers Viscotrol C polyol blend etc.; Be preferable over Viscotrol C, USP Kosher, trihydroxy-polyoxytrimethylene ether, gather hexanodioic acid-1, the mixture of one or more in 4-butanediol ester glycol (PBA), the TriMethylolPropane(TMP) (TMP), total carboxylic monomer amount accounts for 0～45% of total solids quality.
Wherein isocyanate-monomer C is a tolylene diisocyanate (TDI), 4 in the component B described in the step (1); 4 ＇-diphenylmethanediisocyanate (MDI), poly methylene poly phenyl poly isocyanate (PAPI), isophorone diisocyanate (IPDI), hexamethylene diisocyanate (HDI); Be preferable over tolylene diisocyanate (TDI), 4; 4 ＇, one diphenylmethanediisocyanates (MDI); Hexamethylene diisocyanate (HDI), its total isocyanate-monomer amount accounts for 55～100% of total solids quality.
Wherein said catalyzer is organic tin or tertiary amines; Specifically comprise dibutyl tin laurate, stannous octoate, triethylamine, diethylenetriamine, triethylene diamine, TEPA, dimethyl-cetylamine, two dimethyl amine benzyl ethyl ether, nitrogen Ethylmorphine quinoline, trolamine; Thanomin, pyridine or N; N'-lutidine etc., preferred dibutyl tin laurate, diethylenetriamine, triethylene diamine, catalyst levels accounts for 0.05% ~ 0.3% of total solids quality.
Characteristics of the present invention are following: (1) adopts pre-polymerization, crosslinked two step synthesis methods to synthesize the glutinous agent of no-solvent type two-component polyurethane adhesive, simple, the cleaning of production technique, compliance with environmental protection requirements; (2) can regulate the viscosity and the molecular weight of first, second component through pre-polymerization, thereby improve cohesive strength, and cross-linking process can be implemented adhesive solidification, further improves its cohesive strength; (3) first, component B normal temperature is liquid state down, viscosity, adjustable curing speed, and curing reaction at room temperature carries out, and is easy to operate, and energy consumption is low, the product shelf-stable; (4) it is good finally to solidify gained glued membrane snappiness, and mechanical property is excellent, is applicable to the bookbinding of high-grade books.
Better than glued membrane snappiness with the EVA hot melt adhesive, cohesive strength is high, and Amount of spread is merely 1/3 of EVA hot melt adhesive, and need not the heat melten gel, and energy consumption is low; With PUR hot melt adhesive ratio, product stock good stability, automatic double surface gluer requires low, need not sealing, heating, and production cost reduces greatly.
Embodiment
Following embodiment is used to explain the present invention, but never limits range of application of the present invention.
Reference examples:
The preparation of first component
Under the room temperature, 210g Viscotrol C, 30g USP Kosher are added mixing stirring in the reaction vessel, thermostatically heating under 90 ℃ of water bath condition vacuumizes dehydration 1h, and vacuum tightness is-0.095Mpa.Be cooled to 30 ℃, add 10g tolylene diisocyanate (TDI) and stir, slowly be warming up to 70 ℃, behind the reaction 1h, add an amount of di-n-butyltin dilaurate, insulation 1h discharging obtains light yellow, mobile better, transparent thick liquid.
The component B preparation
Under the room temperature, 140g trihydroxy-polyoxytrimethylene ether and 23g USP Kosher are added mixing stirring in the reaction vessel, thermostatically heating under 90 ℃ of water bath condition vacuumizes dehydration 1h, and vacuum tightness is-0.095Mpa.Be cooled to 30 ℃, add 220g tolylene diisocyanate (TDI) mixing and stirring, slowly be warming up to 70 ℃, behind the reaction 3h, obtain the liquid of water white transparency, modest viscosity.
Curing reaction
Under the room temperature, first, second two components of preparation are pressed R=1 mix stirring.
Embodiment 1:
Under the reaction conditions of reference examples, add in addition 100g trihydroxy-polyoxytrimethylene ether in the first component, reaction obtains light yellow, mobile better, transparent thick liquid almost; The amount of trihydroxy-polyoxytrimethylene ether and USP Kosher in the component B is become 105g and 17g respectively, obtain transparent, lurid thick liquid, and first, second two components are pressed R=1.1 mix stirring.
Embodiment 2:
Under the reaction conditions of reference examples; (TDI) replaces with 10g4 with the tolylene diisocyanate in the first component; 4 ＇-diphenylmethanediisocyanate (MDI), reaction obtains light yellow, mobile better, transparent thick liquid, and first, second two components press R=1.2 mix stirring.
Embodiment 3:
Under the reaction conditions of reference examples; Carboxylic monomer in the first component is transformed to 160g Viscotrol C, 20g polyethylene glycol adipate; Isocyanate-monomer is transformed to 10g isophorone diisocyanate (IPDI), obtains the thick liquid light yellow, that viscosity is bigger, transparent; Carboxylic monomer in the component B is transformed to 45g Viscotrol C and 5g USP Kosher, obtain light yellow transparent, than heavy-gravity liquid, and first, second two components are pressed R=1.4 mix to stir.
Embodiment 4:
Under the reaction conditions of reference examples; The amount of the Viscotrol C in the first component is reduced to 200g; Glycerine replaces with 10g trihydroxy-polyoxytrimethylene ether, and isocyanate-monomer becomes 30g isophorone diisocyanate (IPDI), obtains the thick liquid light yellow, that viscosity is big, transparent; Isocyanate-monomer in the component B is transformed to 200g4, and 4 ＇-diphenylmethanediisocyanate (MDI) obtain the liquid of water white transparency, modest viscosity.
Embodiment 5:
Under the condition of reference examples, the isocyanate-monomer in the first component is replaced with 20g4,4 ＇-diphenylmethanediisocyanate (MDI) obtain shallow white, mobile better, translucent thick liquid; The amount of trihydroxy-polyoxytrimethylene ether and USP Kosher in the component B is become 140g and 20g respectively, obtain faint yellow transparent, than heavy-gravity liquid.
Embodiment 6
Under the condition of reference examples, remove the TDI in the first component, and the amount of glycerine is adjusted into 20g, obtain light yellow, translucent heavy-gravity liquid; Carboxylic monomer in the component B is replaced with 5g Viscotrol C and 5g glycerine, and isocyanate-monomer replaces with 200gMDI, obtains water white transparency, than heavy-gravity liquid, and first, second two components is pressed R=0.9 mix and stir.
Embodiment 7
Under the reference examples condition, in the first component, add an amount of triethylene diamine, and the glycerine in the component B is replaced with the 15g TriMethylolPropane(TMP), obtain light yellow, transparent thick liquid.
Embodiment 8
Under the reference examples condition, be the first component with 175g Viscotrol C and 25g glycerine, be the B component with 125gTDI, and first, component B pressed R=1.08 mix stirring.
The performance comparison test
Viscosity: in temperature is under the condition of (25 ± 0.5) ℃, tests according to the mensuration of GB/T2794-1995 tackiness agent viscosity.
Tensile strength: test according to GB/T1040-2006 plastic tensile method for testing performance.
Hardness: test according to the pocket sclerometer penetration hardness of GB/T531-1999 rubber TP.
Shelf lives: the measuring method by GB/T7751-1987 tackiness agent storage period is tested.
*: these data are the laboratory operation data, also can on equipment, regulate in the actual production.
Claims (3)
1. high-grade bookbinding is characterized in that carrying out according to following step with the preparation method of polyurethane adhesive:
(1) prepolymer reaction: with the carboxylic monomer A 1h that under 85 ~ 100 ℃, 0.08 ~ 0.1Mpa vacuum tightness, dewaters, regulate pre-polymerization temperature to 65～90 ℃, add the isocyanate-monomer B and the catalyzer of metering, reaction 2 ~ 3h, synthetic first component; The carboxylic monomer D and the catalyzer that in isocyanate-monomer C, add metering, adjusting pre-polymerization temperature to 70～90 ℃, reaction 2 ~ 3h, synthetic component B;
(2) crosslinking reaction: the first step synthetic first, component B under 25 ℃, is mixed by certain R value mixing, and wherein theoretical R value is 0.9 ~ 1.50, and the R value is the mol ratio of isocyano and hydroxyl; Can obtain high-grade bookbinding and use polyurethane adhesive.
2. high-grade bookbinding according to claim 1 is with the preparation method of polyurethane adhesive, it is characterized in that the carboxylic monomer A in the first component described in the step (1) wherein is polyether polyol, polyester polyol, Viscotrol C, USP Kosher, polyester polyethers polyol blend or polyester Viscotrol C polyol blend, polyethers Viscotrol C polyol blend; Total carboxylic monomer amount accounts for 80～100% of total solids quality;
Wherein the isocyanate-monomer B in the first component described in the step (1) is a tolylene diisocyanate, 4; 4 ＇-diphenylmethanediisocyanate, poly methylene poly phenyl poly isocyanate, isophorone diisocyanate, hexamethylene diisocyanate, its total isocyanate-monomer amount accounts for 0～20% of total solids quality;
Wherein the carboxylic monomer D in the component B described in the step (1) is polyether polyol, polyester polyol, Viscotrol C, USP Kosher, polyester polyethers polyol blend or polyester Viscotrol C polyol blend, polyethers Viscotrol C polyol blend, and total carboxylic monomer amount accounts for 0～45% of total solids quality;
Wherein isocyanate-monomer C is a tolylene diisocyanate, 4 in the component B described in the step (1); 4 ＇-diphenylmethanediisocyanate, poly methylene poly phenyl poly isocyanate, isophorone diisocyanate, hexamethylene diisocyanate, its total isocyanate-monomer amount accounts for 55～100% of total solids quality;
Wherein said catalyzer is organic tin or tertiary amines, and catalyst levels accounts for 0.05% ~ 0.3% of total solids quality.
3. high-grade bookbinding according to claim 2 is with the preparation method of polyurethane adhesive, it is characterized in that carboxylic monomer A in the first component described in the step (1) wherein is one or more the mixture in trihydroxy-polyoxytrimethylene ether, USP Kosher, Viscotrol C, the polyethylene glycol adipate;
Wherein the isocyanate-monomer B in the first component described in the step (1) is tolylene diisocyanate, isophorone diisocyanate, 4,4 ＇-diphenylmethanediisocyanate;
Wherein the carboxylic monomer D in the component B described in the step (1) is Viscotrol C, USP Kosher, trihydroxy-polyoxytrimethylene ether, gathers hexanodioic acid-1, the mixture of one or more in 4-butanediol ester glycol, the TriMethylolPropane(TMP),
Wherein isocyanate-monomer C is tolylene diisocyanate, 4,4 ＇, one diphenylmethanediisocyanate in the component B described in the step (1), hexamethylene diisocyanate;
Wherein said catalyzer is dibutyl tin laurate, stannous octoate, triethylamine, diethylenetriamine, triethylene diamine, TEPA, dimethyl-cetylamine, two dimethyl amine benzyl ethyl ether, nitrogen Ethylmorphine quinoline, trolamine; Thanomin, pyridine or N, the N'-lutidine.
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| Application Number | Priority Date | Filing Date | Title |
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| CN2012101817398A CN102703016A (en) | 2012-06-05 | 2012-06-05 | Preparation method for polyurethane adhesive for binding high-grade books |
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| CN2012101817398A CN102703016A (en) | 2012-06-05 | 2012-06-05 | Preparation method for polyurethane adhesive for binding high-grade books |
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Cited By (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104004490A (en) * | 2014-06-05 | 2014-08-27 | 刘海宁 | Preparation method of compound high molecular adhesive for water permeable brick or water permeable pavement |
| CN105658755A (en) * | 2013-09-27 | 2016-06-08 | Dic株式会社 | Bookbinding adhesive |
| CN106147687A (en) * | 2016-07-05 | 2016-11-23 | 佛山市精信汇明科技有限公司 | A kind of bi-component polyurethane adhesive compound with aluminium for foamed cotton and preparation method thereof |
| CN106905503A (en) * | 2015-12-21 | 2017-06-30 | Dic株式会社 | Polyurethane resin composition and synthetic leather |
| CN107759758A (en) * | 2017-10-31 | 2018-03-06 | 山东诺威聚氨酯股份有限公司 | Low temperature resistant modified polyalcohol and preparation method thereof |
| CN108641345A (en) * | 2018-05-11 | 2018-10-12 | 美瑞新材料股份有限公司 | A kind of TPU film and preparation method thereof with cross-linked structure |
| CN110330627A (en) * | 2019-07-10 | 2019-10-15 | 福建元发树脂有限公司 | Non-solvent single-component polyurethane casting resin |
| CN111019585A (en) * | 2019-12-17 | 2020-04-17 | 烟台德邦科技有限公司 | Double-component reaction type polyurethane hot melt adhesive and preparation method thereof |
| CN111349417A (en) * | 2020-05-07 | 2020-06-30 | 北京天山新材料技术有限公司 | Polyurethane adhesive composition and polyurethane adhesive |
| CN112714699A (en) * | 2019-08-05 | 2021-04-27 | 区敏儿 | Method and apparatus for manufacturing printed product capable of resisting abnormal environmental change and operating all weather and suitable for health management operation, and printed product |
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Cited By (13)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105658755A (en) * | 2013-09-27 | 2016-06-08 | Dic株式会社 | Bookbinding adhesive |
| CN105658755B (en) * | 2013-09-27 | 2017-11-17 | Dic株式会社 | Bookbinding bonding agent |
| CN104004490A (en) * | 2014-06-05 | 2014-08-27 | 刘海宁 | Preparation method of compound high molecular adhesive for water permeable brick or water permeable pavement |
| CN106905503B (en) * | 2015-12-21 | 2020-12-08 | Dic株式会社 | Polyurethane resin composition and synthetic leather |
| CN106905503A (en) * | 2015-12-21 | 2017-06-30 | Dic株式会社 | Polyurethane resin composition and synthetic leather |
| CN106147687A (en) * | 2016-07-05 | 2016-11-23 | 佛山市精信汇明科技有限公司 | A kind of bi-component polyurethane adhesive compound with aluminium for foamed cotton and preparation method thereof |
| CN107759758A (en) * | 2017-10-31 | 2018-03-06 | 山东诺威聚氨酯股份有限公司 | Low temperature resistant modified polyalcohol and preparation method thereof |
| CN108641345A (en) * | 2018-05-11 | 2018-10-12 | 美瑞新材料股份有限公司 | A kind of TPU film and preparation method thereof with cross-linked structure |
| CN108641345B (en) * | 2018-05-11 | 2021-01-19 | 美瑞新材料股份有限公司 | TPU film with cross-linked structure and preparation method thereof |
| CN110330627A (en) * | 2019-07-10 | 2019-10-15 | 福建元发树脂有限公司 | Non-solvent single-component polyurethane casting resin |
| CN112714699A (en) * | 2019-08-05 | 2021-04-27 | 区敏儿 | Method and apparatus for manufacturing printed product capable of resisting abnormal environmental change and operating all weather and suitable for health management operation, and printed product |
| CN111019585A (en) * | 2019-12-17 | 2020-04-17 | 烟台德邦科技有限公司 | Double-component reaction type polyurethane hot melt adhesive and preparation method thereof |
| CN111349417A (en) * | 2020-05-07 | 2020-06-30 | 北京天山新材料技术有限公司 | Polyurethane adhesive composition and polyurethane adhesive |
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Application publication date: 20121003 |