WO2018090182A1 - Degradable adhesive composition and preparation method therefor - Google Patents

Degradable adhesive composition and preparation method therefor Download PDF

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Publication number
WO2018090182A1
WO2018090182A1 PCT/CN2016/105878 CN2016105878W WO2018090182A1 WO 2018090182 A1 WO2018090182 A1 WO 2018090182A1 CN 2016105878 W CN2016105878 W CN 2016105878W WO 2018090182 A1 WO2018090182 A1 WO 2018090182A1
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WIPO (PCT)
Prior art keywords
parts
degradable
adhesive composition
preparation method
degradable adhesive
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Application number
PCT/CN2016/105878
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French (fr)
Chinese (zh)
Inventor
郑健保
莫华
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惠州航程世纪科技有限公司
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Priority to PCT/CN2016/105878 priority Critical patent/WO2018090182A1/en
Publication of WO2018090182A1 publication Critical patent/WO2018090182A1/en

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    • CCHEMISTRY; METALLURGY
    • C09DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09JAdhesives; non-mechanical aspects of adhesive processes in general; adhesive processes not provided for elsewhere; use of material as adhesives
    • C09J123/00Adhesives based on homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Adhesives based on derivatives of such polymers
    • CCHEMISTRY; METALLURGY
    • C09DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09JAdhesives; non-mechanical aspects of adhesive processes in general; adhesive processes not provided for elsewhere; use of material as adhesives
    • C09J131/00Adhesives based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an acyloxy radical of a saturated carboxylic acid, of carbonic acid, or of a haloformic acid; Adhesives based on derivatives of such polymers
    • CCHEMISTRY; METALLURGY
    • C09DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09JAdhesives; non-mechanical aspects of adhesive processes in general; adhesive processes not provided for elsewhere; use of material as adhesives
    • C09J167/00Adhesives based on polyesters obtained by reactions forming a carboxylic ester link in the main chain; Adhesives based on derivatives of such polymers
    • CCHEMISTRY; METALLURGY
    • C09DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09JAdhesives; non-mechanical aspects of adhesive processes in general; adhesive processes not provided for elsewhere; use of material as adhesives
    • C09J175/00Adhesives based on polyureas or polyurethanes; Adhesives based on derivatives of such polymers
    • CCHEMISTRY; METALLURGY
    • C09DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09JAdhesives; non-mechanical aspects of adhesive processes in general; adhesive processes not provided for elsewhere; use of material as adhesives
    • C09J177/00Adhesives based on polyamides obtained by reactions forming a carboxylic amide link in the main chain; Adhesives based on derivatives of such polymers

Abstract

Disclosed is a degradable adhesive composition. The composition consists of the following components in parts by weight: 30 - 80 parts of a degradable polymer, 3 - 9 parts of a tackifier, 10 - 20 parts of an accelerator, 6 - 15 parts of a curing agent, 1 - 5 parts of an antioxidant and 1 - 8 parts of a flame retardant. The preparation method for the composition is as follows: (1) weighing each starting material component in a formulation amount; (2) adding the curing agent to the degradable polymer, heating and slowly stirring same; and (3) successively adding the tackifier, the accelerator, the antioxidant and the flame retardant to step (2), then uniformly stirring, increasing the temperature and keeping the temperature, until same is sol-like. The degradable adhesive composition of the present invention has a good tensile strength, bonding strength and peel strength, and simultaneously also has excellent properties such as an oxidation resistance and fire retardance. The composition has a simple preparation method and a low cost, and is a degradable adhesive which has an excellent comprehensive performance and is environmentally friendly.

Description

Degradable adhesive composition and preparation method thereof Technical field

The invention relates to the field of chemical industry, in particular to the technical field of degradable adhesives, in particular to a degradable adhesive composition and a preparation method thereof.

Background technique

Adhesive refers to a natural or synthetic, organic or inorganic substance that can bond two or more parts or materials together through adhesion and cohesion of the interface. Also known as adhesive, it is customarily referred to as glue. In short, the adhesive is a substance that can bind the adherends by adhesion; the traditional adhesive is used for the purpose of use, the formulation ratio is unreasonable, and the raw materials are wasted.

With the strengthening of people's safety and environmental awareness, research on degradable adhesives has developed rapidly. Degradable adhesive refers to a degradable adhesive formed by dissolving a degradable polymer in water or dispersed in water. It has solvent-free, non-polluting, good film forming properties, strong adhesion, and other polymers compared with solvent type. In particular, the easy blending of the emulsion type polymer is advantageous for the modification. Since the 1990s, it has gradually been applied in automotive interior bonding, kitchen supplies manufacturing, composite film manufacturing, shoe sole bonding, and garment processing. However, there are still many shortcomings, and it is necessary to improve its function through various modifications. For example, Chinese Patent Application No. 200710026211.2 discloses a preparation method of a modified degradable adhesive, which is modified with phosphoric acid or acetic acid to obtain a modified epoxy resin; and polyisocyanate and oligomer Polyol is used as a raw material, and a polyurethane prepolymer is obtained by adding a chain extender; the polyurethane prepolymer is modified with the modified epoxy resin to obtain a modified polyurethane prepolymer, and crosslinking is introduced. Agent and epoxy resin, the cohesive strength and bond strength of the modified degradable adhesive are improved, but the initial tack strength is still poor and the peel strength is still low.

technical problem

The cohesive strength and bond strength of the modified degradable adhesive in the prior art are improved, but the initial tack strength is still poor and the peel strength is still low.

Problem solution

Technical solution

The invention discloses a degradable adhesive composition, which comprises the following components in parts by weight: 30-80 parts of degradable polymer, 3-9 parts of tackifier, 10-20 parts of accelerator, curing 6 to 15 parts of the agent, 1 to 5 parts of the antioxidant, and 1 to 8 parts of the flame retardant;

Further, the degradable polymer is one of polyester, polyurethane, polyamide, ethylene/vinyl acetate, and polyolefin;

Further, the accelerator is one of dibenzothiazyl disulfide, thiuram, dithiocarbamate, and xanthate;

Further, the tackifier is one of rosin-based resin rosin, modified rosin, terpene phenolic resin, Dama resin, Cuban resin, and shellac;

Further, the curing agent is one of ethylenediamine, diethylenetriamine, diaminomethylcyclohexane, and hexahydropyridine;

Further, the antioxidant is diphenylamine, p-phenylenediamine, dihydroquine, (3,5-tris-butyl-4-hydroxyphenyl) sulfide, didodecyl alcohol ester, double fourteen One of a glycol ester and a stearyl alcohol;

Further, the flame retardant is one of aluminum hydroxide, magnesium hydroxide, monoammonium phosphate, diammonium phosphate, ammonium chloride, boric acid, hexabromohydrate, and decabromo-antimony trioxide;

Further, the method for preparing the degradable adhesive composition comprises the following steps:

(1) Weighing the components of the raw materials according to the formula amount;

(2) adding a curing agent to the degradable polymer, heating and stirring slowly;

(3) adding a thickener, a promoter, an antioxidant, and a flame retardant to the step (2), and then uniformly stirring, heating and heating, and then keeping warm until it is in a sol form;

Further, in the stirring state, the heating temperature is 60-80 ° C, and the reaction time is 1-2 hours;

Further, the step (3) is heated to a temperature of 100 to 110 ° C, and the holding time is 20 to 30 minutes.

Advantageous effects of the invention

Beneficial effect

First, the present invention selects a degradable polymer as a main agent, and increases the tensile strength and bond strength of the adhesive by adding a tackifier, a promoter, a curing agent, an antioxidant, a flame retardant and the like. Strong peeling The degree of performance, etc., also makes the adhesive have excellent performance in many aspects such as oxidation resistance and flame retardancy.

Secondly, a curing agent is added to the composition of the present invention to form a network structure between the macromolecular chains in the degradable adhesive, so that the adhesive of the present application also has excellent water resistance, solvent resistance and mechanical properties. The preparation method has the advantages of simple preparation method and low cost, and is a green and environmentally-friendly degradable adhesive with excellent comprehensive performance.

BEST MODE FOR CARRYING OUT THE INVENTION

BEST MODE FOR CARRYING OUT THE INVENTION

The invention discloses a degradable adhesive composition, which comprises the following components in parts by weight: 55 parts of ethylene/vinyl acetate, 7 parts of shellac, 16 parts of xanthate and 11 parts of hexahydropyridine. , 3 parts of dodecanoate, 5 parts of monoammonium phosphate;

The preparation method of the degradable adhesive composition comprises the following steps:

(1) Weighing the components of the raw materials according to the formula amount;

(2) adding ethylene hexahydropyridine to ethylene/vinyl acetate, stirring slowly, heating reaction temperature is 65 ° C, reaction time is 1.5 hours;

(3) Add the shellac, xanthate, dodecyl alcohol ester, and monoammonium phosphate to the step (2), and then uniformly stir, and the temperature is raised to 110 ° C, and then kept for 20 minutes until it is in the form of a sol.

Invention embodiment

Embodiments of the invention

In order to enable those skilled in the art to better understand the technical solutions of the present invention, the technical solutions of the present invention will be further described in detail below with reference to the embodiments.

Example 1

Formulation: a degradable adhesive composition consisting of the following components in parts by weight: 35 parts of polyurethane, 5 parts of terpene phenolic resin, 14 parts of dithiocarbamate, 9 parts of diethylenetriamine 3 parts of didodecanol ester and 6 parts of aluminum hydroxide.

The preparation method of the degradable adhesive composition comprises the following steps:

(1) Weighing the components of the raw materials according to the formula amount;

(2) adding a terpene phenolic resin to the polyurethane, stirring slowly, heating at a reaction temperature of 60 ° C, and a reaction time of 1 hour;

(3) sequentially adding dithiocarbamate, diethylenetriamine, didodecyl alcohol ester, and aluminum hydroxide to step (2), uniformly stirring, heating to 100 ° C, and then keeping warm for 20 minutes until It can be sol-like. The specific parameters of the obtained adhesive are shown in Table 1.

Example 2

Formulation: a degradable adhesive composition composed of the following components in parts by weight: 40 parts of polyester, 6 parts of Dama resin, 15 parts of dibenzothiazole disulfide, 12 parts of ethylenediamine, Ditetradecyl alcohol ester, 2 parts of phenol, and 4 parts of monoammonium phosphate.

The preparation method of the degradable adhesive composition comprises the following steps:

(1) Weighing the components of the raw materials according to the formula amount;

(2) adding Dama resin to the degradable polymer, stirring slowly, heating at a reaction temperature of 70 ° C, and a reaction time of 2 hours;

(3) sequentially adding dibenzothiazyl disulfide, ethylenediamine, ditetradecyl alcohol ester, monoammonium phosphate to step (2), heating to 105 ° C, and then holding for 25 minutes until it is sol-like. . The specific parameters of the obtained adhesive are shown in Table 1.

Example 3

Formulation: The present invention discloses a degradable adhesive composition comprising the following components in parts by weight: ethylene/vinyl acetate 55 parts, shellac 7 parts, xanthate 16 parts, hexahydropyridine 11 parts, 3 parts of dodecanoate, and 5 parts of monoammonium phosphate;

The preparation method of the degradable adhesive composition comprises the following steps:

(1) Weighing the components of the raw materials according to the formula amount;

(2) adding ethylene hexahydropyridine to ethylene/vinyl acetate, stirring slowly, heating reaction temperature is 65 ° C, reaction time is 1.5 hours;

(3) Add the shellac, xanthate, dodecyl alcohol ester, and monoammonium phosphate to the step (2), and then uniformly stir, and the temperature is raised to 110 ° C, and then kept for 20 minutes until it is in the form of a sol. The specific parameters of the obtained adhesive are shown in Table 1.

Example 4

Formulation: The present invention discloses a degradable adhesive composition comprising the following components in parts by weight: 60 parts of polyolefins, 6 parts of Cuban resin, 13 parts of thiuram, diaminomethylcyclohexane 10 parts of alkane, pair 3 parts of phenylenediamine and dihydroquine, and 3 parts of ammonium chloride.

The preparation method of the degradable adhesive composition comprises the following steps:

(1) Weighing the components of the raw materials according to the formula amount;

(2) adding diaminomethylcyclohexane to the degradable polymer, stirring slowly, heating at a reaction temperature of 65 ° C, and a reaction time of 2 hours;

(3) sequentially adding Cuban resin, thiuram, diaminomethylcyclohexane, p-phenylenediamine, dihydroquine, ammonium chloride to step (2), uniformly stirring, heating to 100 ° C, and then holding 30 Minutes, until it is sol-like. The specific parameters of the obtained adhesive are shown in Table 1.

Example 5

The invention discloses a degradable adhesive composition, which comprises the following components in parts by weight: 62 parts of polyamide, 5 parts of modified rosin, 13 parts of dibenzothiazole disulfide, 11 parts of ethylenediamine. 2 parts of ditetradecyl alcohol ester and 5 parts of magnesium hydroxide;

The preparation method of the degradable adhesive composition comprises the following steps:

(1) Weighing the components of the raw materials according to the formula amount;

(2) adding ethylenediamine to the polyamide, stirring slowly, heating the reaction temperature to 70 ° C, the reaction time is 1 hour;

(3) sequentially adding modified rosin, dibenzothiazyl disulfide, ethylenediamine, ditetradecyl alcohol ester, and flame retardant to step (2), uniformly stirring, heating to 110 ° C, and then holding for 25 minutes. It can be until it is in the form of a sol. The specific parameters of the obtained adhesive are shown in Table 1.

Meanwhile, in order to evaluate the specific technical effects of the degradable adhesive composition of the present invention, the products of Examples 1 to 5 were specifically tested from the aspects of tensile bonding, adhesive strength, peel strength, oxidation resistance and the like. . The specific test data is shown in Table 1:

Table 1 specific product performance test data of different examples

Figure PCTCN2016105878-appb-000001

It can be seen from Table 1 that the degradable adhesive composition prepared by the present invention is tested in terms of bond strength, tensile strength, peel strength, and oxidation resistance, and it can be seen that the above data indicate that the present invention is degradable. The adhesive composition has excellent properties, and the preparation method of the composition is simple and easy to obtain, and the cost is low.

The above is only the preferred embodiment of the present invention, and is not intended to limit the present invention in any way; and those skilled in the art can smoothly implement the present invention as described in the specification and described above; The equivalents of some of the changes, modifications and evolutions that can be made by those skilled in the art without departing from the technical scope of the present invention are all equivalent embodiments of the present invention; At the same time, any changes, modifications and evolutions of any equivalent changes made to the above embodiments in accordance with the essential techniques of the present invention are still within the scope of the technical solutions of the present invention.

However, any equivalent changes, modifications, and evolutions that can be made by those skilled in the art without departing from the technical scope of the present invention are equivalent to the present invention. Embodiments; at the same time, any changes, modifications, and evolutions of any equivalent changes made to the above embodiments in accordance with the essential techniques of the present invention are still within the scope of the technical solutions of the present invention.

Industrial applicability

The invention provides a degradable adhesive composition and a preparation method thereof. The degradable adhesive composition has good tensile strength, bond strength and peel strength, and also has excellent properties such as oxidation resistance and flame retardancy.

PCT/CN2016/105878 2016-11-15 2016-11-15 Degradable adhesive composition and preparation method therefor WO2018090182A1 (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
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Application Number Priority Date Filing Date Title
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Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1106440A (en) * 1994-02-03 1995-08-09 山东省招远市合成材料厂 Valve bag binder
CN1294603A (en) * 1998-03-25 2001-05-09 汉高两合股份公司 Polyurethane and prepn. contg. polyurethane
WO2004046214A2 (en) * 2002-10-15 2004-06-03 Exxonmobil Chemical Patents Inc. Multiple catalyst system for olefin polymerization and polymers produced therefrom
CN102007192A (en) * 2008-02-14 2011-04-06 博斯蒂克股份公司 Composition adhesive thermofusible biodegradable
CN104804672A (en) * 2015-04-22 2015-07-29 深圳市沃尔核材股份有限公司 Hot melt adhesive for electric cable accessory of nuclear power station

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1106440A (en) * 1994-02-03 1995-08-09 山东省招远市合成材料厂 Valve bag binder
CN1294603A (en) * 1998-03-25 2001-05-09 汉高两合股份公司 Polyurethane and prepn. contg. polyurethane
WO2004046214A2 (en) * 2002-10-15 2004-06-03 Exxonmobil Chemical Patents Inc. Multiple catalyst system for olefin polymerization and polymers produced therefrom
CN102007192A (en) * 2008-02-14 2011-04-06 博斯蒂克股份公司 Composition adhesive thermofusible biodegradable
CN104804672A (en) * 2015-04-22 2015-07-29 深圳市沃尔核材股份有限公司 Hot melt adhesive for electric cable accessory of nuclear power station

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