阅读说明：本技术 一种改性丁苯压敏胶及其制备方法 (Modified styrene-butadiene pressure-sensitive adhesive and preparation method thereof ) 是由 曹文娟 王欣 刘清钊 牟庆平 任学斌 栾波 于 2020-08-17 设计创作，主要内容包括：本发明属于压敏胶技术领域,尤其涉及一种改性丁苯压敏胶及其制备方法。本发明提供的改性丁苯压敏胶由单体、助剂和水在引发剂作用下反应制成；所述单体包括丁二烯、苯乙烯、酯基单体和松香基衍生物；所述酯基单体包括甲基丙烯酸甲酯、丙烯酸丁酯和丙烯酸-2-羟乙酯中的一种或多种；所述松香基衍生物包括歧化松香、氢化松香、氢化松香季戊四醇酯、聚合松香和松香胺中的一种或多种；所述助剂包括乳化剂、电解质、扩散剂和分子量调节剂。本发明以丁二烯、苯乙烯、酯基单体为主要单体,引入“功能单体”松香基衍生物,用乳液聚合法制得了兼具优异初粘性、持粘性和剥离强度的改性丁苯压敏胶。(The invention belongs to the technical field of pressure-sensitive adhesives, and particularly relates to a modified styrene-butadiene pressure-sensitive adhesive and a preparation method thereof. The modified styrene-butadiene pressure-sensitive adhesive provided by the invention is prepared by reacting a monomer, an auxiliary agent and water under the action of an initiator; the monomer comprises butadiene, styrene, ester group monomer and rosin derivative; the ester group monomer comprises one or more of methyl methacrylate, butyl acrylate and 2-hydroxyethyl acrylate; the rosin-based derivative comprises one or more of disproportionated rosin, hydrogenated rosin pentaerythritol ester, polymerized rosin and rosin amine; the auxiliary agent comprises an emulsifier, an electrolyte, a dispersing agent and a molecular weight regulator. The modified styrene-butadiene pressure-sensitive adhesive with excellent initial adhesion, permanent adhesion and peel strength is prepared by using butadiene, styrene and ester-based monomers as main monomers, introducing a functional monomer rosin-based derivative and using an emulsion polymerization method.)

1. A modified styrene-butadiene pressure-sensitive adhesive is prepared by reacting a monomer, an auxiliary agent and water under the action of an initiator;

the monomer comprises butadiene, styrene, ester group monomer and rosin derivative;

the ester group monomer comprises one or more of methyl methacrylate, butyl acrylate and 2-hydroxyethyl acrylate;

the rosin-based derivative comprises one or more of disproportionated rosin, hydrogenated rosin pentaerythritol ester, polymerized rosin and rosin amine;

the auxiliary agent comprises an emulsifier, an electrolyte, a dispersing agent and a molecular weight regulator.

2. The modified styrene-butadiene pressure-sensitive adhesive according to claim 1, wherein the monomer comprises 60-80 parts by weight of butadiene, 20-40 parts by weight of styrene, 3-10 parts by weight of ester-based monomer and 5-15 parts by weight of rosin-based derivative.

3. The modified styrene-butadiene pressure-sensitive adhesive according to claim 1, wherein the emulsifier comprises one or more of rosin acid soap, linoleate, fatty acid soap and linolenate.

4. The modified styrene-butadiene pressure-sensitive adhesive according to claim 1, wherein the electrolyte comprises one or more of potassium chloride, sodium bicarbonate, sodium hydrogen phosphate and sodium acetate.

5. The modified styrene-butadiene pressure-sensitive adhesive according to claim 1, wherein the dispersing agent comprises one or more of dodecylbenzene sulfonate, a formaldehyde condensate of β -sodium naphthalene sulfonate, sodium diisobutylnaphthalenesulfonate, fatty alcohol-polyoxyethylene ether and polyethylene oxide glycol derivatives.

6. The modified styrene-butadiene pressure-sensitive adhesive according to claim 1, wherein the molecular weight regulator is mercaptan.

7. The modified styrene-butadiene pressure-sensitive adhesive according to claim 1, wherein the initiator comprises one or more of potassium persulfate, ammonium persulfate, sodium persulfate, azodiisobutyronitrile, peroxyacetic acid and benzoyl peroxide.

8. A preparation method of the modified styrene-butadiene pressure-sensitive adhesive of any one of claims 1 to 7 comprises the following steps:

a) mixing butadiene, styrene, ester-based monomer, rosin-based derivative, emulsifier, electrolyte, diffusant, molecular weight regulator and water, and then mixing the obtained mixed system with initiator for reaction to obtain the modified styrene-butadiene pressure-sensitive adhesive.

9. The method of manufacturing according to claim 8, further comprising:

b) mixing the reaction product obtained in the step a) with a terminating agent and an anti-aging agent, and then degassing and filtering to obtain the modified styrene-butadiene pressure-sensitive adhesive.

10. The production method according to claim 9, wherein the terminating agent comprises one or two of sodium ferbamate, hydroquinone, di-tert-butylhydroquinone and dinitrochlorobenzene;

the anti-aging agent comprises one or more of anti-aging agent SP, anti-aging agent TNP and anti-aging agent EPPD.

Technical Field

The invention belongs to the technical field of pressure-sensitive adhesives, and particularly relates to a modified styrene-butadiene pressure-sensitive adhesive and a preparation method thereof.

Background

The pressure-sensitive adhesive is called pressure-sensitive adhesive, adhesive sticker and pressure-sensitive adhesive for short. There are 4 major classes of pressure sensitive adhesives used in industry: solvent-based pressure-sensitive adhesives, emulsion-based pressure-sensitive adhesives, hot-melt pressure-sensitive adhesives and radiation-curable pressure-sensitive adhesives.

In recent years, along with the expansion of the demand of packaging, decoration, office supplies and various labels, the demand of people for pressure-sensitive adhesive is more and more, and the emulsion type pressure-sensitive adhesive is widely applied because of no toxicity and no pollution. At present, the common emulsion type pressure-sensitive adhesives are acrylate emulsion and natural latex pressure-sensitive adhesives, and have the defects of poor initial adhesion, poor permanent adhesion, poor peel strength and the like.

Disclosure of Invention

In view of the above, the present invention provides a modified styrene-butadiene pressure-sensitive adhesive and a preparation method thereof, and the modified styrene-butadiene pressure-sensitive adhesive provided by the invention has excellent initial adhesion, sustained adhesion and peel strength.

The invention provides a modified styrene-butadiene pressure-sensitive adhesive which is prepared by reacting a monomer, an auxiliary agent and water under the action of an initiator;

the monomer comprises butadiene, styrene, ester group monomer and rosin derivative;

the ester group monomer comprises one or more of methyl methacrylate, butyl acrylate and 2-hydroxyethyl acrylate;

the rosin-based derivative comprises one or more of disproportionated rosin, hydrogenated rosin pentaerythritol ester, polymerized rosin and rosin amine;

the auxiliary agent comprises an emulsifier, an electrolyte, a dispersing agent and a molecular weight regulator.

Preferably, the monomer comprises, by weight, 60-80 parts of butadiene, 20-40 parts of styrene, 3-10 parts of an ester-based monomer and 5-15 parts of a rosin-based derivative.

Preferably, the emulsifier comprises one or more of rosin acid soap, linoleate, fatty acid soap and linolenate.

Preferably, the electrolyte comprises one or more of potassium chloride, sodium bicarbonate, sodium hydrogen phosphate and sodium acetate.

Preferably, the dispersing agent comprises one or more of dodecyl benzene sulfonate, a sodium beta-naphthalenesulfonate formaldehyde condensate, sodium diisobutylnaphthalenesulfonate, fatty alcohol-polyoxyethylene ether and polyethylene oxide glycol derivatives.

Preferably, the molecular weight regulator is a thiol.

Preferably, the initiator comprises one or more of potassium persulfate, ammonium persulfate, sodium persulfate, azodiisobutyronitrile, peroxyacetic acid, and benzoyl peroxide.

The invention provides a preparation method of the modified styrene-butadiene pressure-sensitive adhesive in the technical scheme, which comprises the following steps:

a) mixing butadiene, styrene, ester-based monomer, rosin-based derivative, emulsifier, electrolyte, diffusant, molecular weight regulator and water, and then mixing the obtained mixed system with initiator for reaction to obtain the modified styrene-butadiene pressure-sensitive adhesive.

Preferably, the preparation method further comprises:

b) mixing the reaction product obtained in the step a) with a terminating agent and an anti-aging agent, and then degassing and filtering to obtain the modified styrene-butadiene pressure-sensitive adhesive.

Preferably, the terminating agent comprises one or two of sodium dimethyl dithiocarbamate, hydroquinone, di-tert-butylhydroquinone and dinitrochlorobenzene;

the anti-aging agent comprises one or more of anti-aging agent SP, anti-aging agent TNP and anti-aging agent EPPD.

Compared with the prior art, the invention provides a modified styrene-butadiene pressure-sensitive adhesive and a preparation method thereof. The modified styrene-butadiene pressure-sensitive adhesive provided by the invention is prepared by reacting a monomer, an auxiliary agent and water under the action of an initiator; the monomer comprises butadiene, styrene, ester group monomer and rosin derivative; the ester group monomer comprises one or more of methyl methacrylate, butyl acrylate and 2-hydroxyethyl acrylate; the rosin-based derivative comprises one or more of disproportionated rosin, hydrogenated rosin pentaerythritol ester, polymerized rosin and rosin amine; the auxiliary agent comprises an emulsifier, an electrolyte, a dispersing agent and a molecular weight regulator. The invention uses butadiene, styrene and ester group monomer as main monomer, introduces 'functional monomer' rosin derivative, and prepares modified butylbenzene pressure-sensitive adhesive by emulsion polymerization. In the invention, the rosin-based derivative is uniformly dispersed in a styrene-butadiene latex system by adopting an in-situ polymerization mode to form the modified styrene-butadiene pressure-sensitive adhesive taking the rosin-based derivative as a core and taking a styrene-butadiene polymer as a shell, and the modified styrene-butadiene pressure-sensitive adhesive has relatively excellent initial adhesion, lasting adhesion and peel strength. The experimental results show that: the initial adhesion of the modified styrene-butadiene pressure-sensitive adhesive provided by the invention is more than or equal to 10N/cm, the 180-degree stripping force is more than 7N/cm, and the permanent adhesion is more than 36 h.

Detailed Description

The technical solutions in the embodiments of the present invention are clearly and completely described below, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all 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 invention provides a modified styrene-butadiene pressure-sensitive adhesive which is prepared by reacting a monomer, an auxiliary agent and water under the action of an initiator;

the monomer comprises butadiene, styrene, ester group monomer and rosin derivative;

the ester group monomer comprises one or more of methyl methacrylate, butyl acrylate and 2-hydroxyethyl acrylate;

the rosin-based derivative comprises one or more of disproportionated rosin, hydrogenated rosin pentaerythritol ester, polymerized rosin and rosin amine;

the auxiliary agent comprises an emulsifier, an electrolyte, a dispersing agent and a molecular weight regulator.

The modified styrene-butadiene pressure-sensitive adhesive provided by the invention is prepared by reacting a monomer, an auxiliary agent and water under the action of an initiator; more preferably, the rubber composition is prepared by mixing a monomer, an auxiliary agent and water after finishing reaction under the action of an initiator with a terminator and an anti-aging agent, degassing and filtering. Wherein the monomer comprises butadiene, styrene, an ester-based monomer and a rosin-based derivative; the amount of the butadiene is preferably 60 to 80 parts by weight, and specifically may be 60 parts by weight, 61 parts by weight, 62 parts by weight, 63 parts by weight, 64 parts by weight, 65 parts by weight, 66 parts by weight, 67 parts by weight, 68 parts by weight, 69 parts by weight, 70 parts by weight, 71 parts by weight, 72 parts by weight, 73 parts by weight, 74 parts by weight, 75 parts by weight, 76 parts by weight, 77 parts by weight, 78 parts by weight, 79 parts by weight, or 80 parts by weight; the amount of the styrene is preferably 20 to 40 parts by weight, and specifically may be 20 parts by weight, 21 parts by weight, 22 parts by weight, 23 parts by weight, 24 parts by weight, 25 parts by weight, 26 parts by weight, 27 parts by weight, 28 parts by weight, 29 parts by weight, 30 parts by weight, 31 parts by weight, 32 parts by weight, 33 parts by weight, 34 parts by weight, 35 parts by weight, 36 parts by weight, 37 parts by weight, 38 parts by weight, 39 parts by weight, or 40 parts by weight.

In the modified styrene-butadiene pressure-sensitive adhesive provided by the invention, the ester-based monomer comprises one or more of methyl methacrylate, butyl acrylate and 2-hydroxyethyl acrylate; the ester-based monomer is preferably used in an amount of 3 to 10 parts by weight, and specifically may be 3 parts by weight, 4 parts by weight, 5 parts by weight, 6 parts by weight, 7 parts by weight, 8 parts by weight, 9 parts by weight, or 10 parts by weight.

In the modified styrene-butadiene pressure-sensitive adhesive provided by the invention, the rosin-based derivative comprises one or more of disproportionated rosin, hydrogenated rosin pentaerythritol ester, polymerized rosin and rosin amine; the usage amount of the rosin-based derivative is preferably 5 to 15 parts by weight, and specifically may be 5 parts by weight, 6 parts by weight, 7 parts by weight, 8 parts by weight, 9 parts by weight, 10 parts by weight, 11 parts by weight, 12 parts by weight, 13 parts by weight, 14 parts by weight, or 15 parts by weight.

In the modified styrene-butadiene pressure-sensitive adhesive provided by the invention, the auxiliary agent comprises an emulsifier, an electrolyte, a dispersing agent and a molecular weight regulator. Wherein the emulsifier preferably comprises one or more of rosin acid soap, linoleate, fatty acid soap and linolenate; the rosin acid soap is preferably disproportionated potassium rosinate soap; the fatty acid soap is preferably a potassium oleate soap; the emulsifier is preferably used in an amount of 2 to 8 parts by weight, and specifically may be 2 parts by weight, 2.5 parts by weight, 3 parts by weight, 3.5 parts by weight, 4 parts by weight, 4.2 parts by weight, 4.5 parts by weight, 5 parts by weight, 5.5 parts by weight, 6 parts by weight, 6.5 parts by weight, 7 parts by weight, 7.5 parts by weight, or 8 parts by weight. In one embodiment provided herein, the emulsifier comprises rosin acid soap and fatty acid soap; the usage amount of the rosin acid soap is preferably 1.5-5 parts by weight, and specifically may be 1.5 parts by weight, 2 parts by weight, 2.5 parts by weight, 2.7 parts by weight, 3 parts by weight, 3.5 parts by weight, 4 parts by weight, 4.5 parts by weight or 5 parts by weight; the amount of the fatty acid soap is preferably 0.5 to 3 parts by weight, and specifically may be 0.5 part by weight, 1 part by weight, 1.5 parts by weight, 2 parts by weight, 2.5 parts by weight, or 3 parts by weight. In the present invention, the emulsifier is preferably added to the reaction system in the form of an aqueous emulsifier solution, and the concentration of the aqueous emulsifier solution is preferably 25 to 35 wt%, and specifically may be 25 wt%, 26 wt%, 27 wt%, 28 wt%, 29 wt%, 30 wt%, 31 wt%, 32 wt%, 33 wt%, 34 wt%, or 35 wt%.

In the modified styrene-butadiene pressure-sensitive adhesive provided by the invention, the electrolyte preferably comprises one or more of potassium chloride, sodium bicarbonate, sodium hydrogen phosphate and sodium acetate; the amount of the electrolyte is preferably 0.1 to 0.5 parts by weight, and specifically may be 0.1 part by weight, 0.15 part by weight, 0.2 part by weight, 0.25 part by weight, 0.28 part by weight, 0.3 part by weight, 0.35 part by weight, 0.4 part by weight, 0.45 part by weight, or 0.5 part by weight. In the present invention, the electrolyte is preferably added to the reaction system in the form of an aqueous electrolyte solution, and the concentration of the aqueous electrolyte solution is preferably 25 to 35 wt%, and specifically may be 25 wt%, 26 wt%, 27 wt%, 28 wt%, 29 wt%, 30 wt%, 31 wt%, 32 wt%, 33 wt%, 34 wt%, or 35 wt%.

In the modified styrene-butadiene pressure-sensitive adhesive provided by the invention, the diffusant comprises one or more of dodecyl benzene sulfonate, a beta-sodium naphthalene sulfonate formaldehyde condensate, diisobutyl naphthalene sulfonate, fatty alcohol-polyoxyethylene ether and polyethylene oxide glycol derivatives; the polyethylene oxide glycol derivative can be polyethylene oxide sorbitan monooleate; the amount of the dispersing agent is preferably 0.1 to 0.5 part by weight, and specifically may be 0.1 part by weight, 0.15 part by weight, 0.2 part by weight, 0.25 part by weight, 0.3 part by weight, 0.31 part by weight, 0.32 part by weight, 0.35 part by weight, 0.4 part by weight, 0.45 part by weight, or 0.5 part by weight. In the present invention, the diffusing agent is preferably added to the reaction system in the form of a diffusing agent aqueous solution, and the concentration of the diffusing agent aqueous solution is preferably 25 to 35 wt%, and specifically may be 25 wt%, 26 wt%, 27 wt%, 28 wt%, 29 wt%, 30 wt%, 31 wt%, 32 wt%, 33 wt%, 34 wt%, or 35 wt%.

In the modified styrene-butadiene pressure-sensitive adhesive provided by the invention, the molecular weight regulator is preferably mercaptan, more preferably alkyl mercaptan, and most preferably tert-tetradecyl mercaptan; the amount of the molecular weight modifier is preferably 0.1 to 0.5 part by weight, and specifically may be 0.1 part by weight, 0.15 part by weight, 0.2 part by weight, 0.25 part by weight, 0.3 part by weight, 0.35 part by weight, 0.4 part by weight, 0.45 part by weight, or 0.5 part by weight.

In the modified styrene-butadiene pressure-sensitive adhesive provided by the invention, the initiator preferably comprises one or more of potassium persulfate, ammonium persulfate, sodium persulfate, azodiisobutyronitrile, peroxyacetic acid and benzoyl peroxide; the amount of the initiator is preferably 0.1 to 1 part by weight, and specifically may be 0.1 part by weight, 0.2 part by weight, 0.21 part by weight, 0.22 part by weight, 0.25 part by weight, 0.3 part by weight, 0.35 part by weight, 0.4 part by weight, 0.45 part by weight, 0.5 part by weight, 0.6 part by weight, 0.7 part by weight, 0.8 part by weight, 0.9 part by weight, or 1 part by weight.

In the modified styrene-butadiene pressure-sensitive adhesive provided by the invention, the terminator preferably comprises one or two of sodium ferometalate, hydroquinone, di-tert-butylhydroquinone and dinitrochlorobenzene; the amount of the terminator is preferably 0.01 to 0.2 part by weight, and specifically may be 0.01 part by weight, 0.02 part by weight, 0.03 part by weight, 0.04 part by weight, 0.05 part by weight, 0.06 part by weight, 0.07 part by weight, 0.08 part by weight, 0.09 part by weight, 0.1 part by weight, 0.12 part by weight, 0.15 part by weight, 0.17 part by weight, or 0.2 part by weight.

In the modified styrene-butadiene pressure-sensitive adhesive provided by the invention, the anti-aging agent preferably comprises one or more of anti-aging agent SP, anti-aging agent TNP and anti-aging agent EPPD; the antioxidant is preferably used in an amount of 0.1 to 0.3 parts by weight, and specifically may be 0.1 part by weight, 0.12 part by weight, 0.15 part by weight, 0.17 part by weight, 0.2 part by weight, 0.23 part by weight, 0.25 part by weight, 0.27 part by weight, or 0.3 part by weight.

The invention also provides a preparation method of the modified styrene-butadiene pressure-sensitive adhesive in the technical scheme, which comprises the following steps:

a) mixing butadiene, styrene, ester-based monomer, rosin-based derivative, emulsifier, electrolyte, diffusant, molecular weight regulator and water, and then mixing the obtained mixed system with initiator for reaction to obtain the modified styrene-butadiene pressure-sensitive adhesive.

In the preparation method provided by the invention, butadiene, styrene, ester-based monomer, rosin-based derivative, emulsifier, electrolyte, diffusant, molecular weight regulator and water are mixed firstly. Wherein the mixing temperature is preferably 20-40 ℃, and specifically can be 20 ℃, 25 ℃, 30 ℃, 35 ℃ or 40 ℃; the mixing time is preferably 1-3 h, and specifically can be 1h, 1.5h, 2h, 2.5h or 3 h.

In the preparation method provided by the invention, after the components are uniformly mixed, the obtained mixed system is mixed with an initiator for reaction. Wherein the reaction is carried out under oxygen-free conditions; the reaction temperature is preferably 30-70 ℃, and specifically can be 30 ℃, 35 ℃, 40 ℃, 45 ℃, 50 ℃, 55 ℃, 60 ℃, 65 ℃ or 70 ℃; the reaction time is preferably 8-12 h, and specifically can be 8h, 8.5h, 9h, 9.5h, 10h, 10.5h, 11h, 11.5h or 12 h. And after the reaction is finished, obtaining the modified styrene-butadiene pressure-sensitive adhesive provided by the invention.

In the preparation method provided by the invention, in order to remove the insoluble substances in the unreacted monomers and the products, after the reaction is finished, the obtained reaction products are preferably mixed with a terminating agent and an anti-aging agent, and then degassing and filtering are carried out. Wherein the vacuum degree of the degassing is preferably-0.05 to-0.2 MPa, and can be specifically-0.1 MPa; the degassing temperature is preferably 30-50 deg.C, specifically 30 deg.C, 31 deg.C, 32 deg.C, 33 deg.C, 34 deg.C, 35 deg.C, 36 deg.C, 37 deg.C, 38 deg.C, 39 deg.C, 40 deg.C, 41 deg.C, 42 deg.C, 43 deg.C, 44 deg.C, 45 deg.C, 46 deg.C, 47 deg.C, 48 deg.; the degassing time is preferably 0.5-5 h, and specifically can be 0.5h, 1h, 1.5h, 2h, 2.5h, 3h, 3.5h, 4h, 4.5h or 5 h.

The invention uses butadiene, styrene and ester group monomer as main monomer, introduces 'functional monomer' rosin derivative, and prepares modified butylbenzene pressure-sensitive adhesive by emulsion polymerization. In the invention, the rosin-based derivative is uniformly dispersed in a styrene-butadiene latex system by adopting an in-situ polymerization mode to form the modified styrene-butadiene pressure-sensitive adhesive taking the rosin-based derivative as a core and taking a styrene-butadiene polymer as a shell, and the modified styrene-butadiene pressure-sensitive adhesive has relatively excellent initial adhesion, lasting adhesion and peel strength. The experimental results show that: the initial adhesion of the modified styrene-butadiene pressure-sensitive adhesive provided by the invention is more than or equal to 10N/cm, the 180-degree stripping force is more than 7N/cm, and the permanent adhesion is more than 36 h.

For the sake of clarity, the following examples are given in detail.