CN1091129C - High-strength flexible structure adhesive - Google Patents

High-strength flexible structure adhesive Download PDF

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Publication number
CN1091129C
CN1091129C CN97115108A CN97115108A CN1091129C CN 1091129 C CN1091129 C CN 1091129C CN 97115108 A CN97115108 A CN 97115108A CN 97115108 A CN97115108 A CN 97115108A CN 1091129 C CN1091129 C CN 1091129C
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China
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adhesive
modified polyurethane
strength flexible
strength
glue
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CN97115108A
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Chinese (zh)
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CN1206034A (en
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贾剑珉
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贾剑珉
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Abstract

The present invention belongs to the field of polyurethane binder. In order to solve the problems that the cold adhesive has low strength and the hot adhesive damages chemical fibre objects which are adhered, the present invention provides a modified polyurethane structural adhesive which is a blending solidification system which is prepared from poyurethane prepolymer, epoxy resin, polyamide, etc. The present invention has the advantages of strong adhesion force, large shearing resistance, high peel strength, low solidification temperature, short solidification time, long flexure service life, etc., is suitable for glue joint of a high strength fire retardation solid conveying belt with more than 6 level for a mine, the glue joint of various conveying belts and transmission belts, and is also suitable for the adhesive joint of metal and non-metal structural parts which need high strength and also need flexibility.

Description

High-strength flexible structure adhesive
The invention belongs to the modified polyurethane adhesive field.
The at present domestic glue kind that is used for mining flame-retardant integral core conveying belt or the gluing connection of other type conveying belt still is neoprene-that system of tertiary butyl phenol aldehyde-lek, neoprene-PMMA (polymethylmethacrylate)-that system of lek basically, and hot sticky employing and the same or analogous sizing material of adherend melting adhered two big class methods.Adopt neoprene-tertiary butyl phenol aldehyde-lek that, neoprene-PMMA (polymethylmethacrylate)-that system of lek carries out cold bonding, main drawback is that shearing resistance is little, below 10MPa, can not bear the load intensity of high strength integral core conveying belt more than 6 grades basically.For example, 802 seccotines of the at present commercially available new photochemical plant produced in Shanghai, main component is chloroprene rubber and tertiary butyl phenol urea formaldehyde, is mainly used in the bonding of the fire-retardant rubber of needs, leather, fabric, metal.The 861 high-strength plastic main components that Shenyang Institute of Technology produces are chloroprene rubber, tertiary butyl phenol urea formaldehyde and isocyanic ester, are mainly used in bonding conveying belt and metal sheet.These two kinds of glue all can generally solidify 72 hours down at 45 ℃ in room temperature or low-temperature curing, and stripping strength is roughly 50N/cm, and shearing resistance is 4MPa; The fusion hot joining that adopts " similar compatibility " mechanism to carry out, though static strength is higher, but because adherend bears (170-250 ℃ of high temperature action for a long time in the melten gel process, 4-6 hour set time), the knitted body of whole belt core the resinifying phenomenon can partly occur the process that is cooled to normal temperature from intimate molten state, even on the surface of fiber thermal ageing partly, the hardening of belt carcass knitted body is become fragile, deflecting the life-span greatly reduces, that is to say, the method of hot joining has been damaged whole belt core on certain degree, reduced its inherent strength and work-ing life.
For overcoming the deficiencies in the prior art, seek a kind of rubber and plastic bonded structure glue, this structure glue has low surface energy, not only for high energy surface, and polyolefins, the halogen-containing Polymer Surface sticking to difficulty, as PVC, the ideal adhesion is all arranged for chemical fibre classes such as polyamide fibre, terylene; This structure glue also has excellent cohesive strength, and the tension shearing resistance that shows as after following is strong; This structure glue has good visco-elasticity and deflects intensity behind curing cross-linked, the metamorphosis when moving to adapt to adherend; This structure glue also has lower solidification value, is beneficial to not make it impaired because of solidification value is too high when following superpolymer.Thereby this structure glue is specially adapted to the mining splicing of high-strength anti-flaming integral core conveying belt more than 6 grades, and the splicing of other reinforced belt, transmission belt, also is applicable to the bonding of the bonding of metal and nonmetal structure, particularly dynamic structure.
Modified polyurethane high-strength flexible structure adhesive of the present invention is characterized in that it is made up of base polyurethane prepolymer for use as, Resins, epoxy and polymeric amide, wherein, and base polyurethane prepolymer for use as: Resins, epoxy: polymeric amide=30-300: 5-100: 10-500.
Modified polyurethane high-strength flexible structure adhesive of the present invention is to strengthen principle according to interpenetrating(polymer)networks, base polyurethane prepolymer for use as is combined in advance with Resins, epoxy, sneak into polymeric amide then, when above-mentioned ternary blends is heated to 150 ℃, polymeric amide plays the effect of while cured epoxy resin and urethane, thereby, have flexible polyurethane molecular chain and inflexible Resins, epoxy molecular chain and twine, thereby make structure glue of the present invention have the characteristics of high strength and kindliness simultaneously by flexible polymeric amide molecular chain is interspersed mutually.
In modified polyurethane high-strength flexible structure adhesive of the present invention, described base polyurethane prepolymer for use as can be the PAUR performed polymer of isocyanate end or hydroxyl end groups, also can be the Polyether-Polyol Polyurethane Prepolymer of isocyanate end or hydroxyl end groups.Wherein, the PAUR performed polymer with isocyanate end is good.
In modified polyurethane high-strength flexible structure adhesive of the present invention, described Resins, epoxy wherein, is good with bisphenol A epoxide resin.
Modified polyurethane high-strength flexible structure adhesive of the present invention is characterized in that, described polymeric amide comprises the multipolymer or the blend of pure dissolubility polyamide 6, polyamide 66, polymeric amide 11, polymeric amide 12, polyamide 6 10 and Versamid.
Modified polyurethane high-strength flexible structure adhesive of the present invention, it is characterized in that, contain primary amine class solidifying agent in the structure glue component, its consumption is, (be called for short structure glue 1 with the described modified polyurethane high-strength flexible structure adhesive of claim 1, as follows) be 100 (weight parts) meters, then structure glue 1: solidifying agent=100: 0-20 (weight part).
In modified polyurethane high-strength flexible structure adhesive of the present invention, described primary amine class solidifying agent is methylene-bis-o-chloroaniline (MOCA) or Dyhard RU 100.After adding primary amine class solidifying agent, can reduce solidification value effectively, strengthen degree of crosslinking.
Modified polyurethane high-strength flexible structure adhesive of the present invention is characterized in that, contains guanidine class or imidazoles or organic tin or tertiary amine compounds promotor in the structure glue component, and its consumption is structure glue 1: promotor=100: 0-10 (weight part).
In modified polyurethane high-strength flexible structure adhesive of the present invention, described guanidine acclerators is a tetramethyl guanidine, butyl acyl guanidine; Described imidazoles promotor is 2-ethyl 4-methylimidazole; The agent of described organic tin compound promoted is dibutyl tin laurate or stannous octoate; Described tertiary amines promotor is epoxy promotor (DMP-30).After adding promotor, can shorten set time exponentially.
Modified polyurethane high-strength flexible structure adhesive of the present invention is characterized in that, contains titanate coupling agent or silane coupling agent in the structure glue component, and its consumption is structure glue 1: coupling agent=100: 0.1-5 (weight part).The purpose that adds coupling agent is the adhesive power that strengthens tackiness agent, simultaneously to the crosslinked enhancement that also plays between each component of tackiness agent.
Modified polyurethane high-strength flexible structure adhesive of the present invention is characterized in that, contains solvent in the structure glue component, and solvent is one or more the component that is selected from ethyl acetate, butanone, acetone, dithiocarbonic anhydride, methyl alcohol, trieline, the ethylene dichloride.
In modified polyurethane high-strength flexible structure adhesive of the present invention, the consumption of the solvent in its structure glue is structure glue 1: solvent=100: 0-500 (weight part).
In modified polyurethane high-strength flexible structure adhesive of the present invention, generally select ethyl acetate for use, butanone and trieline, three's consumption (weight) ratio is: 60: 40: 100.
In modified polyurethane high-strength flexible structure adhesive of the present invention, if use solidifying agent, promotor, coupling agent, solvent simultaneously, then the workability of structure glue of the present invention is better.
The preparation method of modified polyurethane high-strength flexible structure adhesive of the present invention is: earlier base polyurethane prepolymer for use as is inserted in the reactor, under the agitation condition of heating, slowly add liquid epoxies by the prescription aequum, be incubated 1-8 hour, question response finishes, be cooled to normal temperature, hereinafter to be referred as this mixture is the A component, and the liquid polymeric amide is the B component.During use, get final product in the ratio mixing of A: B=1: 0.5-5 (weight part); Set time and lower solidification value faster if desired, then earlier with required auxiliary material oven dry, weigh by the prescription requirement, then required curing catalyst, solvent are added in the base polyurethane prepolymer for use as of epoxy resin modification as the A component, required solidifying agent, coupling agent, solvent etc. are sneaked in the polymeric amide as the B component, and during use A, B two components being stirred in the ratio of A: B=1: 0.5-5 gets final product.A, can deposit 1 year before B two components are unmixed, after at room temperature mixing, the usage period is 5 hours.
Compared with prior art, the advantage of modified polyurethane high-strength flexible structure adhesive of the present invention is: shearing resistance strengthens several times of (15-35MPa: 4MPa), 90 degree stripping strengths improve tens times of (700N/cm: 50N/cm), the solidification value wide ranges is (by the adjusting to prescription, can make solidification value in room temperature--change in 150 ℃ the zone), set time short (, caning be controlled in 30--240 minute scope) by adjusting to prescription, anti-flexibility strong (deflect life-span 〉=200,000 times).So modified polyurethane high-strength flexible structure adhesive of the present invention is applicable to the mining splicing of high-strength anti-flaming integral core conveying belt more than 6 grades, and the splicing of various reinforced belts, transmission belt, also be applicable to the bonding of the bonding of other metal and nonmetal structure, particularly dynamic structure.
Embodiment: following is embodiments of the invention, is used for without stint explanation the present invention.
Embodiment 1: prepare modified polyurethane high-strength flexible structure adhesive of the present invention by following parts by weight proportioning, wherein, liquid polyurethane performed polymer 100 weight parts, liquid epoxies E44 35 weight parts, liquid epoxies E51 35 weight parts, liquid copolymeric nylon (polymeric amide) 200 weight parts.Condition of cure: contact pressure, 100 ℃/2 hours, 150 ℃/1 hour.Test result: slip resistance 30MPa, 90 degree stripping strength 400N/cm.
Embodiment 2: prepare modified polyurethane high-strength flexible structure adhesive of the present invention by following parts by weight proportioning, wherein, liquid polyurethane performed polymer 100 weight parts, liquid epoxies E44 3 weight parts, liquid epoxies E51 2 weight parts, liquid copolymeric nylon (polymeric amide) 30 weight parts.Condition of cure: contact pressure, 100 ℃/2 hours, 150 ℃/1 hour.Test result: slip resistance 18MPa, 90 degree stripping strength 700N/cm.
Embodiment 3: prepare modified polyurethane high-strength flexible structure adhesive of the present invention by following parts by weight proportioning, wherein, liquid polyurethane performed polymer 100 weight parts, liquid epoxies E51 50 weight parts, liquid copolymeric nylon (polymeric amide) 150 weight parts.Condition of cure: contact pressure, 100 ℃/2 hours, 150 ℃/1 hour.Test result: slip resistance 22MPa, 90 degree stripping strength 600N/cm.
Embodiment 4: prepare modified polyurethane high-strength flexible structure adhesive of the present invention by following parts by weight proportioning, wherein, base polyurethane prepolymer for use as 100 weight parts, Resins, epoxy E44 35 weight parts, Resins, epoxy E51 35 weight parts, liquid copolymeric nylon (polymeric amide) 200 weight parts.Mixed solvent 200 weight parts, wherein: ethyl acetate: butanone: trieline=60: 40: 100.Condition of cure: contact pressure, 100 ℃/2 hours, 150 ℃/1 hour.Test result: slip resistance 30MPa, 90 degree stripping strength 400N/cm.
Embodiment 5: prepare modified polyurethane high-strength flexible structure adhesive of the present invention by following parts by weight proportioning, wherein, base polyurethane prepolymer for use as 100 weight parts, Resins, epoxy E44 35 weight parts, Resins, epoxy E51 35 weight parts, Versamid 200 weight parts, Dyhard RU 100 12 weight parts, tetramethyl guanidine 3 weight parts, titanate coupling agent 2 weight parts.Mixed solvent 200 weight parts, wherein: ethyl acetate: butanone: trieline=60: 40: 100.Condition of cure: contact pressure, 80 ℃/1 hour, 120 ℃/0.5 hour.Test result: slip resistance 28MPa, 90 degree stripping strength 580N/cm.
Mining flame-retardant travelling belt high-strength flexible structure adhesive of the present invention is applicable to the gluing connection of various travelling belts, transmission belt, the particularly gluing connection of the whole core travelling belt of high-strength anti-flaming more than 6 grades, also be applicable to the bonding of the bonding of other metal and nonmetal structure, particularly dynamic structure.

Claims (9)

1, a kind of modified polyurethane high-strength flexible structure adhesive is characterized in that, it is made up of base polyurethane prepolymer for use as, Resins, epoxy and polymeric amide, wherein, and base polyurethane prepolymer for use as: Resins, epoxy: polymeric amide=30-300: 5-100: 10-500.
2, modified polyurethane high-strength flexible structure adhesive as claimed in claim 1, it is characterized in that, described polymeric amide comprises the multipolymer or the blend of pure dissolubility polyamide 6, polyamide 66, polymeric amide 11, polymeric amide 12, polyamide 6 10 and Versamid.
3, modified polyurethane high-strength flexible structure adhesive as claimed in claim 1, it is characterized in that, contain primary amine class solidifying agent in the structure glue component, its consumption is, in the described modified polyurethane high-strength flexible structure adhesive of claim 1 is 100 (weight part), then structure glue: solidifying agent=100: 0-20 (weight part).
4, modified polyurethane high-strength flexible structure adhesive as claimed in claim 3 is characterized in that, described primary amine class solidifying agent is methylene-bis-o-chloroaniline (MOCA) and Dyhard RU 100.
5, modified polyurethane high-strength flexible structure adhesive as claimed in claim 1, it is characterized in that, contain guanidine class or imidazoles organic tin or tertiary amine compounds promotor in the structure glue component, its consumption is, in the described modified polyurethane high-strength flexible structure adhesive of claim 1 is 100 (weight part), then structure glue: promotor=100: 0-10 (weight part).
6, modified polyurethane high-strength flexible structure adhesive as claimed in claim 5 is characterized in that, described guanidine acclerators is a tetramethyl guanidine, butyl acyl guanidine; Described imidazoles promotor is 2-ethyl-4-methylimidazole; The agent of described organic tin compound promoted is dibutyl tin laurate or stannous octoate; Described tertiary amines promotor is epoxy promotor (DMP-30).
7, modified polyurethane high-strength flexible structure adhesive as claimed in claim 1, it is characterized in that, contain titanate coupling agent or silane coupling agent in the structure glue component, its consumption is, in the described modified polyurethane high-strength flexible structure adhesive of claim 1 is 100 (weight part), then structure glue: coupling agent=100: 0.1-5 (weight part).
8, modified polyurethane high-strength flexible structure adhesive as claimed in claim 1, it is characterized in that, also contain solvent in the structure glue component, solvent is one or more the component that is selected from ethyl acetate, butanone, acetone, dithiocarbonic anhydride, methyl alcohol, trieline, the ethylene dichloride.
9, modified polyurethane high-strength flexible structure adhesive as claimed in claim 8, it is characterized in that, the consumption of solvent is in the structure glue component, in the described modified polyurethane high-strength flexible structure adhesive of claim 1 is 100 (weight part), then structure glue: solvent=100: 0-500 (weight part).
CN97115108A 1997-07-21 1997-07-21 High-strength flexible structure adhesive CN1091129C (en)

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CN97115108A CN1091129C (en) 1997-07-21 1997-07-21 High-strength flexible structure adhesive

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CN97115108A CN1091129C (en) 1997-07-21 1997-07-21 High-strength flexible structure adhesive

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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2010097051A1 (en) 2009-02-27 2010-09-02 汉高(中国)投资有限公司 Room-temperature curable epoxy structural adhesive composition and preparation method thereof

Families Citing this family (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1304516C (en) * 2005-12-23 2007-03-14 中冶集团建筑研究总院 Adhesive for slow-binding prestress reinforcement
CN105001820B (en) * 2015-07-07 2017-05-24 广东道氏技术股份有限公司 High-temperature-resisting heat-conducting insulating rubber material and preparation method therefor
CN108865038B (en) * 2017-05-16 2020-05-08 万华化学集团股份有限公司 Isocyanate-based wood adhesive and application method thereof

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1132232A (en) * 1995-03-29 1996-10-02 付玖生 Normal temp. solidified heat risistant rubber for joints connection of conveyer belt
CN1143661A (en) * 1996-01-17 1997-02-26 青岛化工学院 Process for preparing normal temp solidification polyurethane toughened epoxy resin adhesive
CN1144252A (en) * 1994-05-09 1997-03-05 贵州省化工研究院 Polyurethane adhesive

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1144252A (en) * 1994-05-09 1997-03-05 贵州省化工研究院 Polyurethane adhesive
CN1132232A (en) * 1995-03-29 1996-10-02 付玖生 Normal temp. solidified heat risistant rubber for joints connection of conveyer belt
CN1143661A (en) * 1996-01-17 1997-02-26 青岛化工学院 Process for preparing normal temp solidification polyurethane toughened epoxy resin adhesive

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2010097051A1 (en) 2009-02-27 2010-09-02 汉高(中国)投资有限公司 Room-temperature curable epoxy structural adhesive composition and preparation method thereof

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