阅读说明：本技术 一种可降解压敏胶用树脂 (Degradable resin for pressure-sensitive adhesive ) 是由 都佩华 高俊 刘宁宁 秦佳伟 于 2021-02-03 设计创作，主要内容包括：一种可降解压敏胶用树脂,本发明涉及压敏胶技术领域,它由如下摩尔量成分组成：2-羧酸103.0～105.0mol、乙二醇99.0～101.0mol、丙糖1.0mol和聚异氰酸酯1.8～2.2mol。将具有降解性的2-羧酸、乙二醇型脂肪族聚酯和聚异氰酯盐通过附加反应得到的可降解性聚酯聚氨酯,其在自然条件下土壤中无障碍地进行降解,并且再实际运用中具有高粘着力；降解速度快,而且也可调配,耐热性,耐光性,耐气候性好,作为胶水的必要性能即粘着保持力,以及在再剥离时具有高性能的真正可降解压敏胶。(The invention discloses a resin for degradable pressure-sensitive adhesive, which relates to the technical field of pressure-sensitive adhesive and comprises the following components in molar weight: 103.0-105.0 mol of 2-carboxylic acid, 99.0-101.0 mol of ethylene glycol, 1.0mol of triose and 1.8-2.2 mol of polyisocyanate. Degradable polyester polyurethane obtained by carrying out additional reaction on degradable 2-carboxylic acid, ethylene glycol type aliphatic polyester and polyisocyanate salt is degraded in soil without obstacle under natural conditions, and has high adhesive force in actual application; the degradable pressure-sensitive adhesive has high degradation speed, can be prepared, has good heat resistance, light resistance and weather resistance, has the necessary performance of adhesive retention as glue, and has high performance when being peeled off again.)

1. A resin for degradable pressure-sensitive adhesive is characterized in that: the composite material consists of the following components in molar weight: 103.0-105.0 mol of 2-carboxylic acid, 99.0-101.0 mol of ethylene glycol, 1.0mol of triose and 1.8-2.2 mol of polyisocyanate.

2. The resin for a degradable pressure-sensitive adhesive according to claim 1, wherein: the number of alkyl groups of the 2-carboxylic acid is an integer of 2 to 12.

3. The resin for a degradable pressure-sensitive adhesive according to claim 1, wherein: the number of alkyl groups of the ethylene glycol is an integer of 2 to 12, and the side chain group is composed of a material having 1 or more methyl groups or ethyl groups.

4. The resin for a degradable pressure-sensitive adhesive according to claim 1, wherein: the triose is one of trimethylolpropane triacrylate and glycerol.

5. The resin for a degradable pressure-sensitive adhesive according to claim 1, wherein: the ethylene glycol is one or a mixture of more of propylene glycol, 1, 3-butanediol, 1, 4-butanediol, 1, 6-hexanediol and 3-methyl-1, 5-pentanediol.

6. The resin for a degradable pressure-sensitive adhesive according to claim 1, wherein: the polyisocyanate is 1, 6-diethylcyano isocyanate.

7. The resin for a degradable pressure-sensitive adhesive according to claim 1, wherein: the processing method comprises the following steps: adding 103.0-105.0 mol of 2-carboxylic acid, 99.0-101.0 mol of ethylene glycol, 1mol of triose and 0.045-0.055 mol of tetraisopropyl titanate into four 500 ml-mouth separable round-bottom flasks provided with a stirring device, a thermometer, a fractionating pipe and a gas inflow pipe, stirring and heating to 200-220 ℃, and then dehydrating and concentrating; the acid value of the product after 5 hours was 12; changing the shunt tube into a straight-flow tube, and carrying out ethylene glycol removal reaction for 3 hours at the temperature of 200-220 ℃ by using a vacuum pump while reducing the pressure; reducing the pressure to 60Pa finally to obtain a yellowish high-viscosity molten mass; then cooling the high-viscosity molten mass to 180 ℃, returning under normal pressure under the condition of nitrogen flow, adding 0.035-0.045 mol of phosphorous acid, stirring, taking out 125g of reaction resin, and dissolving in 125g of toluene; then adding 3.2g of polyisocyanate under the stirring state at 110 ℃ to carry out chain extension reaction; after cooling, the mixture is diluted by 250g of ethyl acetate to obtain the product.

Technical Field

The invention relates to the technical field of pressure-sensitive adhesives, in particular to a degradable resin for a pressure-sensitive adhesive.

Background

In order to protect the global environment, particularly from the standpoint of avoiding the waste hazard of plastics, degradable resins are widely used. However, in actual use, resin processing agents such as printing, adhesion, and adhesion are essential components, but at present, almost all processing agents are non-degradable processing agents. Originally, polylactic acid and polybutylene succinate, which are biodegradable resins, are crystalline and have a melting point of about 100 ℃ or higher, and thus are not suitable as a resin processing agent. In recent years, in particular, from the viewpoint of convenience of use, when the demand for the adhesive property is expanded, sufficient flexibility and adhesiveness are required for use at room temperature. At present, most of the acrylate-based polymers of the pressure-sensitive adhesive are not degradable, and the pressure-sensitive adhesive used as a degradable resin base material brings inconvenience to the treatment and recycling of degradable wastes if the non-degradable pressure-sensitive adhesive is used. There are those on the market which have degradability mainly made of natural rubber, but natural rubber is not only slow in degradability but also poor in heat resistance, light resistance and season resistance and short in life. Polyesters and polyurethanes using branched bioses have been studied for synthetic products, but these have insufficient adhesive properties, and particularly, they lack a holding power to exhibit adhesive durability, and they are not used because of much residual adhesive during the re-peeling use.

Disclosure of Invention

The invention aims to provide a resin for degradable pressure-sensitive adhesive with reasonable design aiming at the defects and shortcomings of the prior art, which has the advantages of high degradation speed, adjustability, heat resistance, light resistance, good weather resistance, adhesive force of glue and capability of degrading in soil without obstacles under natural conditions; the coating composition can be applied to a base material such as a degradable film, fiber, woven fabric or nonwoven fabric, and can also be used in the fields of adhesive sheets, other dry adhesives and spray coating.

In order to achieve the purpose, the invention adopts the following technical scheme: the composition comprises the following components in parts by weight: the composite material consists of the following components in molar weight: 103.0-105.0 mol of 2-carboxylic acid, 99.0-101.0 mol of ethylene glycol, 1.0mol of triose and 1.8-2.2 mol of polyisocyanate.

Further, the number of alkyl groups of the 2-carboxylic acid is an integer of 2 to 12.

Further, the number of alkyl groups of the ethylene glycol is an integer of 2 to 12, and the side chain group is composed of a material having 1 or more methyl groups or ethyl groups.

Further, the triose is one of trimethylolpropane triacrylate and glycerol.

Furthermore, the ethylene glycol is one or a mixture of more of propylene glycol, 1, 3-butanediol, 1, 4-butanediol, 1, 6-hexanediol and 3-methyl-1, 5-pentanediol.

Further, the polyisocyanate is 1, 6-diethylcyano isocyanate.

The processing method of the invention comprises the following steps: adding 103.0-105.0 mol of 2-carboxylic acid, 99.0-101.0 mol of ethylene glycol, 1mol of triose and 0.045-0.055 mol of tetraisopropyl titanate into four 500 ml-mouth separable round-bottom flasks provided with a stirring device, a thermometer, a fractionating pipe and a gas inflow pipe, stirring and heating to 200-220 ℃, and then dehydrating and concentrating; the acid value of the product after 5 hours was 12; changing the shunt tube into a straight-flow tube, and carrying out ethylene glycol removal reaction for 3 hours at the temperature of 200-220 ℃ by using a vacuum pump while reducing the pressure; reducing the pressure to 60Pa finally to obtain a yellowish high-viscosity molten mass; then cooling the high-viscosity melt to 180 ℃, returning under normal pressure under nitrogen flow, adding 0.035-0.045 mol of phosphorous acid (catalyst) and stirring, taking out 125g of reaction resin, and dissolving in 125g of toluene (diluent solvent) (the device used for dissolving is four 500 ml-mouth separable round-bottom flasks provided with a stirring device, a thermometer, a fractionating tube and a gas inflow tube); then adding 3.2g of polyisocyanate under the stirring state at 110 ℃ to carry out chain extension reaction; after cooling, the mixture was diluted with 250g of ethyl acetate (diluent solvent).

The working principle of the invention is as follows: degradable polyester polyurethane obtained by carrying out additional reaction on degradable 2-carboxylic acid, ethylene glycol type aliphatic polyester and polyisocyanate salt is degraded in soil without obstacle under natural conditions, and has high adhesive force in actual application; that is, the degradable polyester urethane resin having both of the adhesion retention and the non-adhesive property can be used in the fields of an adhesive sheet, other dry adhesives, and spray coating after being coated on a base material such as a degradable film, fiber, woven fabric, or nonwoven fabric. If used as a pressure-sensitive adhesive, a truly degradable pressure-sensitive adhesive which has a high degradation rate and can be formulated, is excellent in heat resistance, light resistance and weather resistance, has a necessary property as a glue, i.e., adhesion retention, and has a high performance at the time of re-peeling.

After the components are adopted, the invention has the beneficial effects that: the resin for the degradable pressure-sensitive adhesive provided by the invention has the advantages of high degradation speed, adjustability, heat resistance, light resistance, good weather resistance, adhesive force of glue and capability of degrading in soil without obstacle under natural conditions; the coating composition can be applied to a base material such as a degradable film, fiber, woven fabric or nonwoven fabric, and can also be used in the fields of adhesive sheets, other dry adhesives and spray coating.

Description of the drawings:

FIG. 1 is a data chart of examples and comparative examples of the present invention.

The specific implementation mode is as follows:

the technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the drawings in the embodiments of the present invention, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all of the embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.

The first embodiment is as follows:

adding 100g of 1, 4-butanediol, 214g of sebacylic acid, 1.42g of trimethylolpropane and 0.15g of tetraisopropyl titanate (catalyst) (the molar ratio of the four is 104:100: 1.0: 0.05) into four 500 ml-mouth separable round-bottom flasks provided with a stirring device, a thermometer, a fractionating tube and a gas inflow tube, stirring and heating to 200-220 ℃, and then dehydrating and concentrating; the acid value of the product after 5 hours was 12; changing the shunt tube into a straight-flow tube, and carrying out ethylene glycol removal reaction for 3 hours at the temperature of 200-220 ℃ by using a vacuum pump while reducing the pressure; reducing the pressure to 60Pa finally to obtain a yellowish high-viscosity molten mass; then cooling the high viscosity melt to 180 ℃, returning under the normal pressure under the nitrogen flow, adding 0.08g of phosphorous acid (catalyst) and stirring, taking out 125g of reaction resin, and dissolving in 125g of toluene (diluent solvent) (the device for dissolving is a four 500 ml-mouth separable round-bottom flask provided with a stirring device, a thermometer, a fractionating tube and a gas inflow tube); then 3.2g of 1, 6-diethylcyano isocyanate is added under the stirring state at 110 ℃ to carry out chain extension reaction; after cooling, the resulting solid resin composition was diluted with 250g of ethyl acetate (diluting solvent) to obtain a solid resin composition having a weight-average molecular weight Mw of about 57 ten thousand, and Tg and Tm of-47.6 ℃ and-23.7 ℃ respectively as measured by DSC; the adhesive force is 1.69N/25mm, the adhesive retention force is 0mm/100 hours, and the residual rates after degradation of the glue after 1 month and 3 months are 15 percent and 2.5 percent respectively.

Example two:

adding 100g of 1, 4-butanediol, 214g of sebacylic acid, 0.98g of glycerol and 0.15g of tetraisopropyl titanate (catalyst) (the molar ratio of the four is 104:100: 1.0: 0.05) into four 500ml round-bottom separable flasks provided with a stirring device, a thermometer, a fractionating tube and a gas inflow tube, stirring and heating to 200-220 ℃, and then dehydrating and concentrating; the acid value of the product after 5 hours was 12; changing the shunt tube into a straight-flow tube, and carrying out ethylene glycol removal reaction for 3 hours at the temperature of 200-220 ℃ by using a vacuum pump while reducing the pressure; reducing the pressure to 60Pa finally to obtain a yellowish high-viscosity molten mass; then cooling the high viscosity melt to 180 ℃, returning under the normal pressure under the nitrogen flow, adding 0.08g of phosphorous acid (catalyst) and stirring, taking out 125g of reaction resin, and dissolving in 125g of toluene (diluent solvent) (the device for dissolving is a four 500 ml-mouth separable round-bottom flask provided with a stirring device, a thermometer, a fractionating tube and a gas inflow tube); then 3.2g of 1, 6-diethylcyano isocyanate is added under the stirring state at 110 ℃ to carry out chain extension reaction; after cooling, the resulting solution was diluted with 250g of ethyl acetate (diluting solvent) to obtain a solid resin component having a weight-average molecular weight Mw of about 53 ten thousand, and Tg and Tm of-48.5 ℃ and-22.0 ℃ respectively as measured by DSC. The adhesive force was 1.92N/25mm, the adhesive holding force was 0mm/100 hours, and the residual rates after degradation after 1 month and 3 months of the glue were 13% and 1.8%, respectively.

Example three:

adding 140g of 1, 4-butanediol, 218.4g of adipic acid, 2g of trimethylolpropane and 0.21g of tetraisopropyl titanate (catalyst) (the molar ratio of the two is 104:100: 1.0: 0.05) into four 500 ml-mouth separable round-bottom flasks provided with a stirring device, a thermometer, a fractionating pipe and a gas inflow pipe, stirring and heating to 200-220 ℃, and then dehydrating and concentrating; the acid value of the product after 5 hours was 14; changing the shunt tube into a straight-flow tube, and carrying out ethylene glycol removal reaction for 3 hours at the temperature of 200-220 ℃ by using a vacuum pump while reducing the pressure; reducing the pressure to 60Pa finally to obtain a yellowish high-viscosity molten mass; then cooling the high viscosity melt to 180 ℃, returning under the normal pressure under the nitrogen flow, adding 0.08g of phosphorous acid (catalyst) and stirring, taking out 125g of reaction resin, and dissolving in 125g of toluene (diluent solvent) (the device for dissolving is a four 500 ml-mouth separable round-bottom flask provided with a stirring device, a thermometer, a fractionating tube and a gas inflow tube); then 3.2g of 1, 6-diethylcyano isocyanate is added under the stirring state at 110 ℃ to carry out chain extension reaction; after cooling, the resulting solution was diluted with 250g of ethyl acetate (diluting solvent) to obtain a solid resin component having a weight-average molecular weight Mw of about 52 ten thousand, and Tg and Tm of-49.8 ℃ and-25.9 ℃ respectively as measured by DSC. The adhesive strength was 2.22N/25mm, the adhesive holding power was 0mm/100 hours, and the residual rates after degradation after 1 month and 3 months of the glue were 9% and 0.9%, respectively.

Comparative example one:

adding 130g of 1, 4-butanediol, 214g of sebacylic acid and 0.12g of tetraisopropyl titanate (catalyst) (the molar ratio of the four is 104:100:0.04) into four 500ml round-bottom separable flasks provided with a stirring device, a thermometer, a fractionating tube and a gas inflow tube, stirring and heating to 200-220 ℃, and then dehydrating and concentrating; the acid value of the product after 5 hours was 12; changing the shunt tube into a straight-flow tube, and carrying out ethylene glycol removal reaction for 3 hours at the temperature of 200-220 ℃ by using a vacuum pump while reducing the pressure; reducing the pressure to 60Pa finally to obtain a yellowish high-viscosity molten mass; then cooling the high viscosity melt to 180 ℃, returning under the normal pressure under the nitrogen flow, adding 0.08g of phosphorous acid (catalyst) and stirring, taking out 125g of reaction resin, and dissolving in 125g of toluene (diluent solvent) (the device for dissolving is a four 500 ml-mouth separable round-bottom flask provided with a stirring device, a thermometer, a fractionating tube and a gas inflow tube); then 3.2g of 1, 6-diethylcyano isocyanate is added under the stirring state at 110 ℃ to carry out chain extension reaction; after cooling, the resulting solid resin composition was diluted with 250g of ethyl acetate (diluting solvent) to obtain a solid resin composition having a weight-average molecular weight Mw of about 47 ten thousand, and Tg and Tm of-47.2 ℃ and-21.5 ℃ respectively as measured by DSC; the adhesive force is 4.5N/25mm, the adhesive retention force is 0mm/100 hours, and the residual rates after degradation of the glue after 1 month and 3 months are respectively 16% and 3.8%.

Comparative example two:

adding 130g of 1, 4-butanediol, 249.6g of oxalic acid, 0.23g of trimethylolpropane and 0.19g of tetraisopropyl titanate (catalyst) into four 500 ml-mouth separable round-bottom flasks provided with a stirring device, a thermometer, a fractionating tube and a gas inflow tube (the molar ratio of the four is 104:100:0.1:0.04), stirring and heating to 200-220 ℃, and then dehydrating and concentrating; the acid value of the product after 5 hours was 12; changing the shunt tube into a straight-flow tube, and carrying out ethylene glycol removal reaction for 3 hours at the temperature of 200-220 ℃ by using a vacuum pump while reducing the pressure; reducing the pressure to 60Pa finally to obtain a yellowish high-viscosity molten mass; then cooling the high viscosity melt to 180 ℃, returning under the normal pressure under the nitrogen flow, adding 0.08g of phosphorous acid (catalyst) and stirring, taking out 125g of reaction resin, and dissolving in 125g of toluene (diluent solvent) (the device for dissolving is a four 500 ml-mouth separable round-bottom flask provided with a stirring device, a thermometer, a fractionating tube and a gas inflow tube); then 3.2g of 1, 6-diethylcyano isocyanate is added under the stirring state at 110 ℃ to carry out chain extension reaction; after cooling, the resulting solid resin composition was diluted with 250g of ethyl acetate (diluting solvent) to obtain a solid resin composition having a weight-average molecular weight Mw of about 44 ten thousand, and Tg and Tm of-29.1 ℃ and-15.5 ℃ respectively as measured by DSC; since the solid resin component crystallizes at normal temperature, a resin whose viscosity cannot be measured is formed.

Comparative example three:

adding 130g of 3-methyl-1, 5-pentanediol, 214g of sebacylic acid, 2g of trimethylolpropane and 0.129g of tetraisopropyl titanate (catalyst) into four 500ml round-bottom separable flasks provided with a stirring device, a thermometer, a fractionating tube and a gas inflow tube (the molar ratio of the four is 104:100:0.1:0.04), stirring and heating to 200-220 ℃, and then dehydrating and concentrating; the acid value of the product after 5 hours was 14; changing the shunt tube into a straight-flow tube, and carrying out ethylene glycol removal reaction for 3 hours at the temperature of 200-220 ℃ by using a vacuum pump while reducing the pressure; reducing the pressure to 60Pa finally to obtain a yellowish high-viscosity molten mass; then cooling the high viscosity melt to 180 ℃, returning under the normal pressure under the nitrogen flow, adding 0.08g of phosphorous acid (catalyst) and stirring, taking out 125g of reaction resin, and dissolving in 125g of toluene (diluent solvent) (the device for dissolving is a four 500 ml-mouth separable round-bottom flask provided with a stirring device, a thermometer, a fractionating tube and a gas inflow tube); then 1.86g of 1, 6-diethylcyano isocyanate is added under the stirring state at 110 ℃ to carry out chain extension reaction; after cooling, the resulting solution was diluted with 250g of ethyl acetate (diluting solvent) to obtain a solid resin component having a weight-average molecular weight Mw of about 33 ten thousand, and Tg and Tm as measured by DSC of-40.2 ℃ and-21.3 ℃. The adhesive force was 5.13N/25mm, the adhesive holding force was 0mm/100 hours, and the residual rates after degradation after 1 month and 3 months of the glue were 12% and 2.1%, respectively.

Referring to fig. 1, the resin prepared in the first to third embodiments has better residual glue evaluation and lower residual rate after degradation.

The working principle of the specific embodiment is as follows: degradable polyester polyurethane obtained by carrying out additional reaction on degradable 2-carboxylic acid, ethylene glycol type aliphatic polyester and polyisocyanate salt is degraded in soil without obstacle under natural conditions, and has high adhesive force in actual application; that is, the degradable polyester urethane resin having both of the adhesion retention and the non-adhesive property can be used in the fields of an adhesive sheet, other dry adhesives, and spray coating after being coated on a base material such as a degradable film, fiber, woven fabric, or nonwoven fabric. If used as a pressure-sensitive adhesive, a truly degradable pressure-sensitive adhesive which has a high degradation rate and can be formulated, is excellent in heat resistance, light resistance and weather resistance, has a necessary property as a glue, i.e., adhesion retention, and has a high performance at the time of re-peeling.

After the components are adopted, the beneficial effects of the specific embodiment are as follows: the specific embodiment provides the resin for the degradable pressure-sensitive adhesive, which has the advantages of high degradation speed, adjustability, heat resistance, light resistance, good weather resistance, adhesive force of glue and capability of degrading in soil without obstacle under natural conditions; the coating composition can be applied to a base material such as a degradable film, fiber, woven fabric or nonwoven fabric, and can also be used in the fields of adhesive sheets, other dry adhesives and spray coating.

Although the present invention has been described in detail with reference to the foregoing embodiments, it will be apparent to those skilled in the art that various changes in the embodiments and/or modifications of the invention can be made, and equivalents and modifications of some features of the invention can be made without departing from the spirit and scope of the invention.