CN111534256A - Low-sensitization medical acrylate pressure-sensitive adhesive and preparation method thereof - Google Patents

Low-sensitization medical acrylate pressure-sensitive adhesive and preparation method thereof Download PDF

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CN111534256A
CN111534256A CN202010467329.4A CN202010467329A CN111534256A CN 111534256 A CN111534256 A CN 111534256A CN 202010467329 A CN202010467329 A CN 202010467329A CN 111534256 A CN111534256 A CN 111534256A
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sensitive adhesive
acrylate
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weight
monomer
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郭敏杰
郑娜
王家泰
周文雅
马转弟
王子珍
高天娇
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Tianjin University of Science and Technology
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Tianjin University of Science and Technology
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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 MATERIALS AS ADHESIVES
    • C09J133/00Adhesives 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 only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Adhesives based on derivatives of such polymers
    • C09J133/04Homopolymers or copolymers of esters
    • C09J133/06Homopolymers or copolymers of esters of esters containing only carbon, hydrogen and oxygen, the oxygen atom being present only as part of the carboxyl radical
    • C09J133/062Copolymers with monomers not covered by C09J133/06
    • C09J133/064Copolymers with monomers not covered by C09J133/06 containing anhydride, COOH or COOM groups, with M being metal or onium-cation
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    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08FMACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F2/00Processes of polymerisation
    • C08F2/12Polymerisation in non-solvents
    • C08F2/16Aqueous medium
    • C08F2/22Emulsion polymerisation
    • C08F2/24Emulsion polymerisation with the aid of emulsifying agents
    • C08F2/26Emulsion polymerisation with the aid of emulsifying agents anionic
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    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08FMACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F220/00Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
    • C08F220/02Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
    • C08F220/10Esters
    • C08F220/12Esters of monohydric alcohols or phenols
    • C08F220/16Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms
    • C08F220/18Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms with acrylic or methacrylic acids
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    • 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 MATERIALS AS ADHESIVES
    • C09J133/00Adhesives 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 only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Adhesives based on derivatives of such polymers
    • C09J133/04Homopolymers or copolymers of esters
    • C09J133/06Homopolymers or copolymers of esters of esters containing only carbon, hydrogen and oxygen, the oxygen atom being present only as part of the carboxyl radical
    • C09J133/062Copolymers with monomers not covered by C09J133/06
    • C09J133/066Copolymers with monomers not covered by C09J133/06 containing -OH groups
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    • 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 MATERIALS AS ADHESIVES
    • C09J133/00Adhesives 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 only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Adhesives based on derivatives of such polymers
    • C09J133/04Homopolymers or copolymers of esters
    • C09J133/06Homopolymers or copolymers of esters of esters containing only carbon, hydrogen and oxygen, the oxygen atom being present only as part of the carboxyl radical
    • C09J133/08Homopolymers or copolymers of acrylic acid esters
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    • C09J133/00Adhesives 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 only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Adhesives based on derivatives of such polymers
    • C09J133/18Homopolymers or copolymers of nitriles
    • C09J133/20Homopolymers or copolymers of acrylonitrile
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    • 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 MATERIALS AS ADHESIVES
    • C09J133/00Adhesives 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 only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Adhesives based on derivatives of such polymers
    • C09J133/24Homopolymers or copolymers of amides or imides
    • C09J133/26Homopolymers or copolymers of acrylamide or methacrylamide
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    • C09DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
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    • C09J7/00Adhesives in the form of films or foils
    • C09J7/30Adhesives in the form of films or foils characterised by the adhesive composition
    • C09J7/38Pressure-sensitive adhesives [PSA]
    • C09J7/381Pressure-sensitive adhesives [PSA] based on macromolecular compounds obtained by reactions involving only carbon-to-carbon unsaturated bonds
    • C09J7/385Acrylic polymers

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  • Organic Chemistry (AREA)
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  • Polymers & Plastics (AREA)
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Abstract

The invention discloses a hypoallergenic medical acrylate pressure-sensitive adhesive, which comprises 75-90 parts by weight of soft monomers, 10-25 parts by weight of hard monomers, 0.2-0.7 part by weight of initiators, 1-3 parts by weight of emulsifiers, 0.1-0.2 part by weight of buffers, 90-110 parts by weight of deionized water and selectively-added functional monomers; the soft monomer is butyl acrylate and/or isooctyl acrylate; the hard monomer is methyl methacrylate, methyl acrylate, vinyl acetate, styrene, acrylonitrile or acrylamide; the low-sensitization medical acrylate pressure-sensitive adhesive is a medical adhesive product with good biocompatibility, low sensitization, no residue after stripping and no skin tearing injury, and is suitable for infants, old people and patients with poor skin conditions; in the preparation method, the seed semi-continuous emulsion polymerization is adopted, the monomer conversion rate is reduced effectively, the monomer residual rate is reduced, and the method has the characteristics of no toxicity, safe production and small environmental pollution, and has good economic benefit and practicability.

Description

Low-sensitization medical acrylate pressure-sensitive adhesive and preparation method thereof
Technical Field
The invention relates to the technical field of pressure-sensitive adhesives, in particular to a low-sensitization medical acrylate pressure-sensitive adhesive and a preparation method thereof.
Background
The pressure-sensitive adhesive is an adhesive which can wet the adhered surface and firmly adhere an adhered object by applying a certain pressure to generate adhesive strength, has the characteristics of easy adhesion, difficult uncovering, peeling without damage, no dry and solid adhesive layer in a long time, simple and convenient use and the like, and is widely applied to various fields of industry, daily use, medical use and the like. The medical pressure-sensitive adhesive has higher requirements on the performance of the pressure-sensitive adhesive and needs to meet the following requirements: (1) the bonding performance is excellent; (2) when peeled off from the skin, the skin-care product does not leave any residual glue or cause skin damage and does not irritate the skin. The acrylate medical pressure-sensitive adhesive has good viscosity and can be repeatedly stripped, so that the acrylate medical pressure-sensitive adhesive is widely applied to the medical field.
Medical adhesive-related Skin lesions (Medical adhesive-related Skin lesions): the removal of the medical adhesive can be continued for 30min or more for erythema or other skin disorder (such as blister, bulla, laceration, maceration, etc.). Infants, the elderly, and people with skin damage have a high susceptibility to skin damage, and are at high risk for MARSI. MARSI causes pain to elderly patients, increases the risk of infection, enlarges wound area, affects healing, thereby affecting the quality of life of the patient, and increases hospitalization costs for the patient.
When a medical pressure-sensitive adhesive is used, if the adhesion between the skin and the pressure-sensitive adhesive is higher than the adhesion between skin cells, partial or complete separation of the epidermis layer of the skin occurs upon removal, resulting in damage to the skin surface. The most common types of MARSI in infants and the elderly are mainly mechanical lesions (exfoliation of the epidermis, laceration of the skin, tension lesions or blisters), dermatitis (contact dermatitis, allergic dermatitis).
From a chemical point of view to address MARSI: first, the most common forms of exfoliation and skin tearing in the elderly and infants are caused by too high peel strength of the medical pressure sensitive adhesive used. 2. Contact dermatitis is caused by low conversion rate of pressure-sensitive adhesive and high monomer residue.
The acrylate pressure-sensitive adhesive on the market at present has high bonding strength, and is very easy to cause tearing injury to skin particularly when the peel strength is high. Secondly, in order to make the pressure-sensitive adhesive have higher mechanical property, the pressure-sensitive adhesive on the market is prepared by mixing five or six or even more monomers, and thickening agents and the like are added in some pressure-sensitive adhesives, so that the monomer conversion rate is low, the monomers are easy to remain, and the allergy phenomenon is easy to generate for the old, children and people with skin injury.
Disclosure of Invention
The invention aims to provide the low-sensitization medical acrylate pressure-sensitive adhesive which has good biocompatibility, low sensitization, moderate stripping strength, no residue in stripping and simple formula.
Therefore, the technical scheme of the invention is as follows:
a low-sensitization medical acrylate pressure-sensitive adhesive comprises 75-90 parts by weight of soft monomers, 10-25 parts by weight of hard monomers, 0.2-0.7 part by weight of initiators, 1-3 parts by weight of emulsifiers, 0.1-0.2 part by weight of buffering agents and 90-110 parts by weight of deionized water; wherein the soft monomer is an acrylate substance prepared by the reaction of acrylic acid and alcohol with 4-8 carbon atoms; the hard monomer is methyl methacrylate, methyl acrylate, vinyl acetate, styrene, acrylonitrile or acrylamide.
Preferably, the soft monomer is butyl acrylate or isooctyl acrylate. More preferably, the soft monomer is butyl acrylate.
Preferably, the hard monomer is methyl methacrylate.
Preferably, the hypoallergenic medical acrylate pressure-sensitive adhesive also comprises 3-7 parts of functional monomers; the functional monomer is acrylic acid, hydroxyethyl acrylate or hydroxypropyl acrylate. More preferably, the functional monomer is hydroxyethyl acrylate.
Preferably, the initiator is potassium persulfate or ammonium persulfate.
Preferably, the emulsifier is sodium lauryl sulfate.
Preferably, the buffer is a carbonate or phosphate; more preferably, the buffer is sodium bicarbonate or sodium dihydrogen phosphate.
A preparation method of low-sensitization medical acrylate pressure-sensitive adhesive comprises the following steps:
step A, preparation stage: adding part of the emulsifier and all the buffering agent into a reaction container, adding part of deionized water, stirring and dissolving, heating to 55-65 ℃, and keeping the temperature for 30-40 min; wherein the addition amount of the emulsifier is 10-30% of the total weight of the emulsifier;
step B, a seed stage: continuously heating the mixed solution obtained in the step A to 65-75 ℃, dropwise adding part of seed monomers and initiator aqueous solution into the reaction container in the step A at a constant speed under the condition of stirring, preserving heat for 50-90 min after dropwise adding is finished, and dropwise adding the rest emulsifier aqueous solution into the reaction container in the step A when the heat preservation process is carried out for 25-45 min; wherein the feeding amount of the seed monomer is 5-20% of the total weight of the monomer; the feeding amount of the initiator is 5-20% of the total weight of the initiator;
step C, a feeding stage: continuously heating the mixed solution obtained in the step B to 75-80 ℃, dropwise adding the residual initiator aqueous solution and the residual monomers into the reaction container in the step A at a constant speed under the stirring condition, and keeping the temperature unchanged in the dropwise adding process;
step D, heat preservation reaction: and C, continuously heating the mixed solution obtained in the step C to 80-85 ℃, preserving the heat for 1-1.5 hours under the stirring condition, then cooling, and discharging.
Preferably, in the step A to the step D, the stirring speed is 250 to 400 rpm.
Compared with the prior art, the low-sensitization medical acrylate pressure-sensitive adhesive does not contain auxiliary agents such as tackifying resin, softening agent, anti-aging agent, thickening agent and the like in the preparation formula, is a medical adhesive product with good biocompatibility, low sensitization, no residue after stripping and no skin tearing, has excellent viscosity, and is suitable for infants, old people and patients with poor skin conditions; in terms of the preparation method, the hypoallergenic medical acrylate pressure-sensitive adhesive adopts seed semi-continuous emulsion polymerization, so that the monomer conversion rate effectively reduces the monomer residual rate; and in the preparation process, an organic solvent is not needed, so that the preparation method has the characteristics of no toxicity, safety in production and small environmental pollution, and has good economic benefit and practicability.
Detailed Description
The present invention will be further described with reference to the following examples, which are not intended to limit the invention in any way.
Example 1
The hypoallergenic medical acrylate pressure-sensitive adhesive comprises the following raw materials in parts by weight: 90 parts of butyl acrylate, 10 parts of methyl methacrylate, 7 parts of acrylic acid, 0.2 part of potassium persulfate, 3 parts of sodium dodecyl sulfate, 0.1 part of sodium bicarbonate and 100 parts of deionized water;
the preparation method of the hypoallergenic medical acrylate pressure-sensitive adhesive comprises the following steps:
step A, preparation stage: adding part of sodium dodecyl sulfate and all sodium bicarbonate into a reaction vessel, adding part of deionized water, stirring and dissolving, heating to 55 ℃, and keeping the temperature for 30 min; wherein, the addition amount of the emulsifier is 10 percent of the total weight of the emulsifier;
step B, a seed stage: continuously heating the mixed solution obtained in the step A to 65 ℃, dropwise adding part of butyl acrylate, methyl methacrylate, acrylic acid and part of potassium persulfate aqueous solution into the reaction container in the step A at a constant speed under the condition of stirring, preserving the heat for 50min after completing dropwise adding, and dropwise adding the rest of sodium dodecyl sulfate aqueous solution into the reaction container in the step A when the heat preservation process is carried out for 25 min; wherein, in the step, the feeding amount of the butyl acrylate, the methyl methacrylate and the acrylic acid is respectively 5 percent of the total weight of the butyl acrylate, the methyl methacrylate and the acrylic acid, and the feeding amount of the potassium persulfate aqueous solution is 5 percent of the total weight of the potassium persulfate aqueous solution;
step C, a feeding stage: continuously heating the mixed solution obtained in the step B to 75 ℃, dropwise adding the residual butyl acrylate, methyl methacrylate, acrylic acid and the residual potassium persulfate aqueous solution into the reaction container in the step A at a constant speed under the stirring condition, and keeping the temperature unchanged in the dropwise adding process;
step D, heat preservation reaction: c, continuously heating the mixed solution obtained in the step C to 80 ℃, preserving the temperature for 1h under the stirring condition, then performing cooling treatment, and discharging to obtain the hypoallergenic medical acrylate pressure-sensitive adhesive;
in steps A to D, the stirring speed was 250 rpm.
Example 2
The hypoallergenic medical acrylate pressure-sensitive adhesive comprises the following raw materials in parts by weight: 90 parts of butyl acrylate, 10 parts of methyl methacrylate, 0.3 part of potassium persulfate, 1.5 parts of lauryl sodium sulfate, 0.2 part of sodium bicarbonate and 100 parts of deionized water;
the preparation method of the hypoallergenic medical acrylate pressure-sensitive adhesive comprises the following steps:
step A, preparation stage: adding part of sodium dodecyl sulfate and all sodium bicarbonate into a reaction vessel, adding part of deionized water, stirring and dissolving, heating to 60 ℃, and preserving heat for 40 min; wherein the addition amount of the emulsifier is 15 percent of the total weight of the emulsifier;
step B, a seed stage: continuously heating the mixed solution obtained in the step A to 70 ℃, dropwise adding part of butyl acrylate, methyl methacrylate and part of potassium persulfate aqueous solution into the reaction container in the step A at a constant speed under the condition of stirring, preserving the temperature for 80min after finishing dropwise adding, and dropwise adding the rest of sodium dodecyl sulfate aqueous solution into the reaction container in the step A when the temperature preserving process is carried out for 40 min; wherein, in the step, the feeding amount of the butyl acrylate, the methyl methacrylate and the acrylic acid is respectively 15 percent of the total weight of the butyl acrylate, the methyl methacrylate and the acrylic acid, and the feeding amount of the potassium persulfate aqueous solution is 15 percent of the total weight of the potassium persulfate aqueous solution;
step C, a feeding stage: continuously heating the mixed solution obtained in the step B to 78 ℃, dropwise adding the rest butyl acrylate, the rest methyl methacrylate and the rest potassium persulfate aqueous solution into the reaction container in the step A at a constant speed under the stirring condition, continuously stirring in the dropwise adding process, and keeping the temperature unchanged;
step D, heat preservation reaction: c, continuously heating the mixed solution obtained in the step C to 83 ℃, preserving heat for 1h under the stirring condition, then performing cooling treatment, and discharging to obtain the hypoallergenic medical acrylate pressure-sensitive adhesive;
in steps A to D, the stirring speed was 300 rpm.
Example 3
The hypoallergenic medical acrylate pressure-sensitive adhesive comprises the following raw materials in parts by weight: 90 parts of butyl acrylate, 10 parts of methyl methacrylate, 0.4 part of potassium persulfate, 2 parts of lauryl sodium sulfate, 0.1 part of sodium bicarbonate and 100 parts of deionized water;
the preparation method of the hypoallergenic medical acrylate pressure-sensitive adhesive comprises the following steps:
step A, preparation stage: adding part of sodium dodecyl sulfate and all sodium bicarbonate into a reaction vessel, adding part of deionized water, stirring and dissolving, heating to 60 ℃, and preserving heat for 40 min; wherein the addition amount of the emulsifier is 20 percent of the total weight of the emulsifier;
step B, a seed stage: continuously heating the mixed solution obtained in the step A to 70 ℃, dropwise adding part of butyl acrylate, methyl methacrylate and part of potassium persulfate aqueous solution into the reaction container in the step A at a constant speed under the condition of stirring, preserving the temperature for 80min after finishing dropwise adding, and dropwise adding the rest of sodium dodecyl sulfate aqueous solution into the reaction container in the step A when the temperature preserving process is carried out for 40 min; wherein, in the step, the feeding amount of the butyl acrylate, the methyl methacrylate and the acrylic acid is respectively 10 percent of the total weight of the butyl acrylate, the methyl methacrylate and the acrylic acid, and the feeding amount of the potassium persulfate aqueous solution is 10 percent of the total weight of the potassium persulfate aqueous solution;
step C, a feeding stage: continuously heating the mixed solution obtained in the step B to 78 ℃, dropwise adding the rest butyl acrylate, the rest methyl methacrylate and the rest potassium persulfate aqueous solution into the reaction container in the step A at a constant speed under the stirring condition, continuously stirring in the dropwise adding process, and keeping the temperature unchanged;
step D, heat preservation reaction: c, continuously heating the mixed solution obtained in the step C to 83 ℃, preserving heat for 1h under the stirring condition, then performing cooling treatment, and discharging to obtain the hypoallergenic medical acrylate pressure-sensitive adhesive;
in steps A to D, the stirring speed was 300 rpm.
Example 4
The hypoallergenic medical acrylate pressure-sensitive adhesive comprises the following raw materials in parts by weight: 80 parts of butyl acrylate, 20 parts of vinyl acetate, 3 parts of hydroxypropyl acrylate, 0.5 part of potassium persulfate, 2.5 parts of sodium dodecyl sulfate, 0.1 part of sodium dihydrogen phosphate and 100 parts of deionized water;
the preparation method of the hypoallergenic medical acrylate pressure-sensitive adhesive comprises the following steps:
step A, preparation stage: adding part of sodium dodecyl sulfate and all sodium dihydrogen phosphate into a reaction vessel, adding part of deionized water, stirring to dissolve, heating to 65 ℃, and keeping the temperature for 35 min; wherein, the addition amount of the emulsifier is 30 percent of the total weight of the emulsifier;
step B, a seed stage: continuously heating the mixed solution obtained in the step A to 75 ℃, dropwise adding part of butyl acrylate, vinyl acetate, hydroxypropyl acrylate and part of potassium persulfate aqueous solution into the reaction container in the step A at a constant speed under the condition of stirring, preserving the temperature for 90min after dropwise adding is finished, and dropwise adding the rest of sodium dodecyl sulfate aqueous solution into the reaction container in the step A when the temperature is preserved for 45 min; wherein, in the step, the feeding amount of butyl acrylate, vinyl acetate and hydroxypropyl acrylate is respectively 15 percent of the total weight of the butyl acrylate, the vinyl acetate and the hydroxypropyl acrylate, and the feeding amount of the potassium persulfate aqueous solution is 15 percent of the total weight of the potassium persulfate aqueous solution;
step C, a feeding stage: continuously heating the mixed solution obtained in the step B to 80 ℃, dropwise adding the rest butyl acrylate, vinyl acetate, hydroxypropyl acrylate and the rest potassium persulfate aqueous solution into the reaction container in the step A at a constant speed under the stirring condition, continuously stirring in the dropwise adding process, and keeping the temperature unchanged;
step D, heat preservation reaction: c, continuously heating the mixed solution obtained in the step C to 85 ℃, preserving the heat for 1.5 hours under the stirring condition, then performing cooling treatment, and discharging to obtain the hypoallergenic medical acrylate pressure-sensitive adhesive;
in the steps A to D, the stirring speed was 350 rpm.
Example 5
The hypoallergenic medical acrylate pressure-sensitive adhesive comprises the following raw materials in parts by weight: 60 parts of butyl acrylate, 30 parts of isooctyl acrylate, 10 parts of styrene, 0.7 part of potassium persulfate, 3 parts of sodium dodecyl sulfate, 0.1 part of sodium dihydrogen phosphate and 100 parts of deionized water;
the preparation method of the hypoallergenic medical acrylate pressure-sensitive adhesive comprises the following steps:
step A, preparation stage: adding part of sodium dodecyl sulfate and all sodium dihydrogen phosphate into a reaction vessel, adding part of deionized water, stirring to dissolve, heating to 65 ℃, and keeping the temperature for 35 min; wherein, the addition amount of the emulsifier is 30 percent of the total weight of the emulsifier;
step B, a seed stage: continuously heating the mixed solution obtained in the step A to 75 ℃, dropwise adding part of butyl acrylate, isooctyl acrylate, styrene and part of potassium persulfate aqueous solution into the reaction container in the step A at a constant speed under the stirring condition, preserving the temperature for 70min after completing dropwise adding, and dropwise adding the rest of sodium dodecyl sulfate aqueous solution into the reaction container in the step A when the temperature preserving process is carried out for 35 min; in the step, the feeding amount of butyl acrylate, isooctyl acrylate and styrene is respectively 20 percent of the total weight of the butyl acrylate, isooctyl acrylate and styrene, and the feeding amount of the potassium persulfate aqueous solution is 20 percent of the total weight of the potassium persulfate aqueous solution;
step C, a feeding stage: continuously heating the mixed solution obtained in the step B to 80 ℃, dropwise adding the rest butyl acrylate, isooctyl acrylate, styrene and the rest potassium persulfate aqueous solution into the reaction container in the step A at a constant speed under the stirring condition, continuously stirring in the dropwise adding process, and keeping the temperature unchanged;
step D, heat preservation reaction: c, continuously heating the mixed solution obtained in the step C to 85 ℃, preserving the heat for 1.5 hours under the stirring condition, then performing cooling treatment, and discharging to obtain the hypoallergenic medical acrylate pressure-sensitive adhesive;
in steps A to D, the stirring speed was 400 rpm.
Example 6
The hypoallergenic medical acrylate pressure-sensitive adhesive comprises the following raw materials in parts by weight: 87 parts of butyl acrylate, 13 parts of methyl methacrylate, 0.4 part of potassium persulfate, 1.5 parts of sodium dodecyl sulfate, 0.1 part of sodium bicarbonate and 110 parts of deionized water;
the preparation method of the hypoallergenic medical acrylate pressure-sensitive adhesive comprises the following steps:
step A, preparation stage: adding part of sodium dodecyl sulfate and all sodium bicarbonate into a reaction vessel, adding part of deionized water, stirring and dissolving, heating to 60 ℃, and preserving heat for 40 min; wherein the addition amount of the emulsifier is 20 percent of the total weight of the emulsifier;
step B, a seed stage: continuously heating the mixed solution obtained in the step A to 65 ℃, dropwise adding part of butyl acrylate, methyl methacrylate and part of potassium persulfate aqueous solution into the reaction container in the step A at a constant speed under the condition of stirring, preserving the temperature for 80min after finishing dropwise adding, and dropwise adding the rest of sodium dodecyl sulfate aqueous solution into the reaction container in the step A when the temperature preserving process is carried out for 40 min; in the step, the feeding amount of butyl acrylate and methyl methacrylate is respectively 10% of the total weight of the butyl acrylate and the methyl methacrylate, and the feeding amount of the potassium persulfate aqueous solution is 10% of the total weight of the potassium persulfate aqueous solution;
step C, a feeding stage: continuously heating the mixed solution obtained in the step B to 80 ℃, dropwise adding the rest butyl acrylate, the rest methyl methacrylate and the rest potassium persulfate aqueous solution into the reaction container in the step A at a constant speed under the stirring condition, continuously stirring in the dropwise adding process, and keeping the temperature unchanged;
step D, heat preservation reaction: c, continuously heating the mixed solution obtained in the step C to 85 ℃, preserving the temperature for 1h under the stirring condition, then performing cooling treatment, and discharging to obtain the hypoallergenic medical acrylate pressure-sensitive adhesive;
in the steps A to D, the stirring speed was 350 rpm.
Example 7
The hypoallergenic medical acrylate pressure-sensitive adhesive comprises the following raw materials in parts by weight: 75 parts of butyl acrylate, 25 parts of methyl methacrylate, 0.4 part of ammonium persulfate, 1.5 parts of lauryl sodium sulfate, 0.1 part of sodium bicarbonate and 100 parts of deionized water;
the preparation method of the hypoallergenic medical acrylate pressure-sensitive adhesive comprises the following steps:
step A, preparation stage: adding part of sodium dodecyl sulfate and all sodium bicarbonate into a reaction vessel, adding part of deionized water, stirring and dissolving, heating to 60 ℃, and preserving heat for 40 min; wherein the addition amount of the emulsifier is 15 percent of the total weight of the emulsifier;
step B, a seed stage: continuously heating the mixed solution obtained in the step A to 75 ℃, dropwise adding part of butyl acrylate, methyl methacrylate and part of ammonium persulfate aqueous solution into the reaction container in the step A at a constant speed under the condition of stirring, preserving the heat for 80min after completing dropwise adding, and dropwise adding the rest of sodium dodecyl sulfate aqueous solution into the reaction container in the step A when the heat preservation process is carried out for 40 min; in the step, the feeding amount of butyl acrylate and methyl methacrylate is respectively 10% of the total weight of the butyl acrylate and the methyl methacrylate, and the feeding amount of the ammonium persulfate aqueous solution is 10% of the total weight of the ammonium persulfate aqueous solution;
step C, a feeding stage: continuously heating the mixed solution obtained in the step B to 80 ℃, dissolving the rest butyl acrylate, methyl methacrylate and the rest ammonium persulfate aqueous solution in the rest deionized water under the stirring condition, dropwise adding the mixture into the reaction container in the step A at a constant speed under the stirring condition, continuously stirring the mixture in the dropwise adding process, and keeping the temperature unchanged;
step D, heat preservation reaction: c, continuously heating the mixed solution obtained in the step C to 85 ℃, preserving the temperature for 1h under the stirring condition, then performing cooling treatment, and discharging to obtain the hypoallergenic medical acrylate pressure-sensitive adhesive;
in the steps A to D, the stirring speed was 350 rpm.
Example 8
The hypoallergenic medical acrylate pressure-sensitive adhesive comprises the following raw materials in parts by weight: 90 parts of butyl acrylate, 10 parts of methyl methacrylate, 7 parts of acrylic acid, 0.7 part of potassium persulfate, 3 parts of sodium dodecyl sulfate, 0.1 part of sodium bicarbonate and 100 parts of deionized water;
the preparation method of the hypoallergenic medical acrylate pressure-sensitive adhesive comprises the following steps:
step A, preparation stage: adding part of sodium dodecyl sulfate and all sodium bicarbonate into a reaction vessel, adding part of deionized water, stirring and dissolving, heating to 60 ℃, and preserving heat for 40 min; wherein the addition amount of the emulsifier is 20 percent of the total weight of the emulsifier;
step B, a seed stage: continuously heating the mixed solution obtained in the step A to 75 ℃, dropwise adding part of butyl acrylate, methyl methacrylate, acrylic acid and part of potassium persulfate aqueous solution into the reaction container in the step A at a constant speed under the condition of stirring, preserving the temperature for 90min after finishing dropwise adding, and dropwise adding the rest of sodium dodecyl sulfate aqueous solution into the reaction container in the step A when the temperature is preserved for 45 min; in the step, the feeding amount of butyl acrylate, methyl methacrylate and acrylic acid is respectively 15% of the total weight of the butyl acrylate, the methyl methacrylate and the acrylic acid, and the feeding amount of the potassium persulfate aqueous solution is 15% of the total weight of the potassium persulfate aqueous solution;
step C, a feeding stage: continuously heating the mixed solution obtained in the step B to 80 ℃, dropwise adding the rest butyl acrylate, methyl methacrylate, acrylic acid and the rest potassium persulfate aqueous solution into the reaction container in the step A at a constant speed under the stirring condition, continuously stirring in the dropwise adding process, and keeping the temperature unchanged;
step D, heat preservation reaction: c, continuously heating the mixed solution obtained in the step C to 85 ℃, preserving the temperature for 1h under the stirring condition, then performing cooling treatment, and discharging to obtain the hypoallergenic medical acrylate pressure-sensitive adhesive;
in the steps A to D, the stirring speed was 350 rpm.
Example 9
The hypoallergenic medical acrylate pressure-sensitive adhesive comprises the following raw materials in parts by weight: 90 parts of butyl acrylate, 10 parts of methyl methacrylate, 0.4 part of potassium persulfate, 2.5 parts of sodium dodecyl sulfate, 0.1 part of sodium bicarbonate and 100 parts of deionized water;
the preparation method of the hypoallergenic medical acrylate pressure-sensitive adhesive comprises the following steps:
step A, preparation stage: adding part of sodium dodecyl sulfate and all sodium bicarbonate into a reaction vessel, adding part of deionized water, stirring and dissolving, heating to 60 ℃, and preserving heat for 40 min; wherein the addition amount of the emulsifier is 20 percent of the total weight of the emulsifier;
step B, a seed stage: continuously heating the mixed solution obtained in the step A to 75 ℃, dropwise adding part of butyl acrylate, methyl methacrylate and part of potassium persulfate aqueous solution into the reaction container in the step A at a constant speed under the condition of stirring, preserving the temperature for 80min after completing dropwise adding, and respectively setting the feeding amount of the residual sodium dodecyl sulfate aqueous solution acrylic acid as 10% of the total weight of the sodium dodecyl sulfate aqueous solution acrylic acid and the feeding amount of the potassium persulfate aqueous solution as 10% of the total weight of the potassium persulfate aqueous solution at the 40min of the heat preservation process;
step C, a feeding stage: continuously heating the mixed solution obtained in the step B to 80 ℃, dropwise adding the rest butyl acrylate, the rest methyl methacrylate and the rest potassium persulfate aqueous solution into the reaction container in the step A at a constant speed under the stirring condition, continuously stirring in the dropwise adding process, and keeping the temperature unchanged;
step D, heat preservation reaction: c, continuously heating the mixed solution obtained in the step C to 85 ℃, preserving the temperature for 1h under the stirring condition, then performing cooling treatment, and discharging to obtain the hypoallergenic medical acrylate pressure-sensitive adhesive;
in steps A to D, the stirring speed was 300 rpm.
Example 10
The hypoallergenic medical acrylate pressure-sensitive adhesive comprises the following raw materials in parts by weight: 85 parts of butyl acrylate, 15 parts of acrylonitrile, 3 parts of hydroxypropyl acrylate, 0.7 part of potassium persulfate, 2.5 parts of sodium dodecyl sulfate, 0.2 part of sodium dihydrogen phosphate and 100 parts of deionized water;
the preparation method of the hypoallergenic medical acrylate pressure-sensitive adhesive comprises the following steps:
step A, preparation stage: adding part of sodium dodecyl sulfate and all sodium dihydrogen phosphate into a reaction vessel, adding part of deionized water, stirring to dissolve, heating to 65 ℃, and keeping the temperature for 40 min; wherein, the addition amount of the emulsifier is 25 percent of the total weight of the emulsifier;
step B, a seed stage: continuously heating the mixed solution obtained in the step A to 70 ℃, dropwise adding part of butyl acrylate, acrylonitrile, hydroxypropyl acrylate and part of potassium persulfate aqueous solution into the reaction container in the step A at a constant speed under the condition of stirring, preserving the temperature for 90min after finishing dropwise adding, and dropwise adding the rest of sodium dodecyl sulfate aqueous solution into the reaction container in the step A when the temperature is preserved for 45 min; in the step, the feeding amount of butyl acrylate, acrylonitrile and hydroxypropyl acrylate is respectively 20% of the total weight of the butyl acrylate, the acrylonitrile and the hydroxypropyl acrylate, and the feeding amount of the potassium persulfate aqueous solution is 20% of the total weight of the potassium persulfate aqueous solution;
step C, a feeding stage: continuously heating the mixed solution obtained in the step B to 75 ℃, dropwise adding the rest butyl acrylate, the acrylonitrile, the hydroxypropyl acrylate and the rest potassium persulfate aqueous solution into the reaction container in the step A at a constant speed under the stirring condition, continuously stirring in the dropwise adding process, and keeping the temperature unchanged;
step D, heat preservation reaction: c, continuously heating the mixed solution obtained in the step C to 80 ℃, preserving the temperature for 1h under the stirring condition, then performing cooling treatment, and discharging to obtain the hypoallergenic medical acrylate pressure-sensitive adhesive;
in steps A to D, the stirring speed was 400 rpm.
Example 11
The hypoallergenic medical acrylate pressure-sensitive adhesive comprises the following raw materials in parts by weight: 90 parts of butyl acrylate, 10 parts of methyl methacrylate, 0.4 part of potassium persulfate, 1.5 parts of lauryl sodium sulfate, 0.1 part of sodium bicarbonate and 100 parts of deionized water;
the preparation method of the hypoallergenic medical acrylate pressure-sensitive adhesive comprises the following steps:
step A, preparation stage: adding part of sodium dodecyl sulfate and all sodium bicarbonate into a reaction vessel, adding part of deionized water, stirring and dissolving, heating to 60 ℃, and preserving heat for 40 min; wherein the addition amount of the emulsifier is 20 percent of the total weight of the emulsifier;
step B, a seed stage: continuously heating the mixed solution obtained in the step A to 75 ℃, dropwise adding part of butyl acrylate, methyl methacrylate and part of potassium persulfate aqueous solution into the reaction container in the step A at a constant speed under the condition of stirring, preserving the temperature for 80min after finishing dropwise adding, and dropwise adding the rest of sodium dodecyl sulfate aqueous solution into the reaction container in the step A when the temperature preserving process is carried out for 40 min; in the step, the feeding amount of butyl acrylate and methyl methacrylate is respectively 10% of the total weight of the butyl acrylate and the methyl methacrylate, and the feeding amount of the potassium persulfate aqueous solution is 10% of the total weight of the potassium persulfate aqueous solution;
step C, a feeding stage: continuously heating the mixed solution obtained in the step B to 80 ℃, dropwise adding the rest butyl acrylate, the rest methyl methacrylate and the rest potassium persulfate aqueous solution into the reaction container in the step A at a constant speed under the stirring condition, continuously stirring in the dropwise adding process, and keeping the temperature unchanged;
step D, heat preservation reaction: c, continuously heating the mixed solution obtained in the step C to 85 ℃, preserving the temperature for 1h under the stirring condition, then performing cooling treatment, and discharging to obtain the hypoallergenic medical acrylate pressure-sensitive adhesive;
in steps A to D, the stirring speed was 300 rpm.
Example 12
The hypoallergenic medical acrylate pressure-sensitive adhesive comprises the following raw materials in parts by weight: 90 parts of butyl acrylate, 10 parts of methyl methacrylate, 0.4 part of potassium persulfate, 1 part of lauryl sodium sulfate, 0.1 part of sodium bicarbonate and 100 parts of deionized water;
the preparation method of the hypoallergenic medical acrylate pressure-sensitive adhesive comprises the following steps:
step A, preparation stage: adding part of sodium dodecyl sulfate and all sodium bicarbonate into a reaction vessel, adding part of deionized water, stirring and dissolving, heating to 60 ℃, and preserving heat for 40 min; wherein the addition amount of the emulsifier is 20 percent of the total weight of the emulsifier;
step B, a seed stage: continuously heating the mixed solution obtained in the step A to 75 ℃, dropwise adding part of butyl acrylate, methyl methacrylate and part of potassium persulfate aqueous solution into the reaction container in the step A at a constant speed under the condition of stirring, preserving the temperature for 80min after finishing dropwise adding, and dropwise adding the rest of sodium dodecyl sulfate aqueous solution into the reaction container in the step A when the temperature preserving process is carried out for 40 min; in the step, the feeding amount of butyl acrylate and methyl methacrylate is respectively 10% of the total weight of the butyl acrylate and the methyl methacrylate, and the feeding amount of the potassium persulfate aqueous solution is 10% of the total weight of the potassium persulfate aqueous solution;
step C, a feeding stage: continuously heating the mixed solution obtained in the step B to 80 ℃, dropwise adding the rest butyl acrylate, the rest methyl methacrylate and the rest potassium persulfate aqueous solution into the reaction container in the step A at a constant speed under the stirring condition, continuously stirring in the dropwise adding process, and keeping the temperature unchanged;
step D, heat preservation reaction: c, continuously heating the mixed solution obtained in the step C to 85 ℃, preserving the temperature for 1h under the stirring condition, then performing cooling treatment, and discharging to obtain the hypoallergenic medical acrylate pressure-sensitive adhesive;
in steps A to D, the stirring speed was 300 rpm.
Example 13
The hypoallergenic medical acrylate pressure-sensitive adhesive comprises the following raw materials in parts by weight: 60 parts of butyl acrylate, 30 parts of isooctyl acrylate, 10 parts of acrylamide, 0.2 part of ammonium persulfate, 1.5 parts of sodium dodecyl sulfate, 0.1 part of sodium bicarbonate and 100 parts of deionized water;
the preparation method of the hypoallergenic medical acrylate pressure-sensitive adhesive comprises the following steps:
step A, preparation stage: adding part of sodium dodecyl sulfate and all sodium bicarbonate into a reaction vessel, adding part of deionized water, stirring and dissolving, heating to 60 ℃, and preserving heat for 40 min; wherein the addition amount of the emulsifier is 20 percent of the total weight of the emulsifier;
step B, a seed stage: continuously heating the mixed solution obtained in the step A to 75 ℃, dropwise adding part of butyl acrylate, isooctyl acrylate, acrylamide and part of ammonium persulfate aqueous solution into the reaction container in the step A at a constant speed under the condition of stirring, preserving the heat for 80min after completing dropwise adding, and dropwise adding the rest of sodium dodecyl sulfate aqueous solution into the reaction container in the step A when the heat preservation process is carried out for 40 min; in the step, the feeding amount of butyl acrylate, isooctyl acrylate and acrylamide is respectively 20% of the total weight of the butyl acrylate, isooctyl acrylate and acrylamide, and the feeding amount of the ammonium persulfate aqueous solution is 20% of the total weight of the ammonium persulfate aqueous solution;
step C, a feeding stage: continuously heating the mixed solution obtained in the step B to 80 ℃, dropwise adding the rest butyl acrylate, isooctyl acrylate, acrylamide and the rest ammonium persulfate aqueous solution into the reaction container in the step A at a constant speed under the stirring condition, continuously stirring in the dropwise adding process, and keeping the temperature unchanged;
step D, heat preservation reaction: c, continuously heating the mixed solution obtained in the step C to 85 ℃, preserving the heat for 1.5 hours under the stirring condition, then performing cooling treatment, and discharging to obtain the hypoallergenic medical acrylate pressure-sensitive adhesive;
in the steps A to D, the stirring speed was 350 rpm.
Example 14
The hypoallergenic medical acrylate pressure-sensitive adhesive comprises the following raw materials in parts by weight: 78 parts of butyl acrylate, 22 parts of methyl methacrylate, 3 parts of hydroxyethyl acrylate, 0.4 part of potassium persulfate, 2 parts of sodium dodecyl sulfate, 0.1 part of sodium bicarbonate and 100 parts of deionized water;
the preparation method of the hypoallergenic medical acrylate pressure-sensitive adhesive comprises the following steps:
step A, preparation stage: adding part of sodium dodecyl sulfate and all sodium bicarbonate into a reaction vessel, adding part of deionized water, stirring and dissolving, heating to 60 ℃, and preserving heat for 40 min; wherein, the addition amount of the emulsifier is 25 percent of the total weight of the emulsifier;
step B, a seed stage: continuously heating the mixed solution obtained in the step A to 75 ℃, dropwise adding part of butyl acrylate, methyl methacrylate, hydroxyethyl acrylate and part of potassium persulfate aqueous solution into the reaction container in the step A at a constant speed under the stirring condition, preserving the temperature for 80min after completing dropwise adding, and dropwise adding the rest of sodium dodecyl sulfate aqueous solution into the reaction container in the step A when the temperature is preserved for 40 min; in the step, the feeding amount of butyl acrylate, methyl methacrylate and hydroxyethyl acrylate is respectively 15% of the total weight of the aqueous potassium persulfate solution, and the feeding amount of the aqueous potassium persulfate solution is 15% of the total weight of the aqueous potassium persulfate solution;
step C, a feeding stage: continuously heating the mixed solution obtained in the step B to 80 ℃, dropwise adding the rest butyl acrylate, methyl methacrylate, hydroxyethyl acrylate and the rest potassium persulfate aqueous solution into the reaction container in the step A at a constant speed under the stirring condition, continuously stirring in the dropwise adding process, and keeping the temperature unchanged;
step D, heat preservation reaction: c, continuously heating the mixed solution obtained in the step C to 85 ℃, preserving the temperature for 1h under the stirring condition, then performing cooling treatment, and discharging to obtain the hypoallergenic medical acrylate pressure-sensitive adhesive;
in steps A to D, the stirring speed was 300 rpm.
Example 15
The hypoallergenic medical acrylate pressure-sensitive adhesive comprises the following raw materials in parts by weight: 78 parts of butyl acrylate, 22 parts of methyl methacrylate, 4 parts of hydroxyethyl acrylate, 0.4 part of potassium persulfate, 2 parts of sodium dodecyl sulfate, 0.1 part of sodium bicarbonate and 100 parts of deionized water;
the preparation method of the hypoallergenic medical acrylate pressure-sensitive adhesive comprises the following steps:
step A, preparation stage: adding part of sodium dodecyl sulfate and all sodium bicarbonate into a reaction vessel, adding part of deionized water, stirring and dissolving, heating to 65 ℃, and keeping the temperature for 40 min; wherein, the addition amount of the emulsifier is 25 percent of the total weight of the emulsifier;
step B, a seed stage: continuously heating the mixed solution obtained in the step A to 75 ℃, dropwise adding part of butyl acrylate, methyl methacrylate, hydroxyethyl acrylate and part of potassium persulfate aqueous solution into the reaction container in the step A at a constant speed under the stirring condition, preserving the temperature for 80min after completing dropwise adding, and dropwise adding the rest of sodium dodecyl sulfate aqueous solution into the reaction container in the step A when the temperature is preserved for 40 min; in the step, the feeding amount of butyl acrylate, methyl methacrylate and hydroxyethyl acrylate is respectively 15% of the total weight of the aqueous potassium persulfate solution, and the feeding amount of the aqueous potassium persulfate solution is 15% of the total weight of the aqueous potassium persulfate solution;
step C, a feeding stage: continuously heating the mixed solution obtained in the step B to 80 ℃, dropwise adding the rest butyl acrylate, methyl methacrylate, hydroxyethyl acrylate and the rest potassium persulfate aqueous solution into the reaction container in the step A at a constant speed under the stirring condition, continuously stirring in the dropwise adding process, and keeping the temperature unchanged;
step D, heat preservation reaction: c, continuously heating the mixed solution obtained in the step C to 85 ℃, preserving the temperature for 1h under the stirring condition, then performing cooling treatment, and discharging to obtain the hypoallergenic medical acrylate pressure-sensitive adhesive;
in steps A to D, the stirring speed was 300 rpm.
Example 16
The hypoallergenic medical acrylate pressure-sensitive adhesive comprises the following raw materials in parts by weight: 78 parts of butyl acrylate, 22 parts of methyl methacrylate, 6 parts of hydroxyethyl acrylate, 0.4 part of potassium persulfate, 2 parts of sodium dodecyl sulfate, 0.1 part of sodium bicarbonate and 100 parts of deionized water;
the preparation method of the hypoallergenic medical acrylate pressure-sensitive adhesive comprises the following steps:
step A, preparation stage: adding part of sodium dodecyl sulfate and all sodium bicarbonate into a reaction vessel, adding part of deionized water, stirring and dissolving, heating to 65 ℃, and keeping the temperature for 40 min; wherein, the addition amount of the emulsifier is 25 percent of the total weight of the emulsifier;
step B, a seed stage: continuously heating the mixed solution obtained in the step A to 75 ℃, dropwise adding part of butyl acrylate, methyl methacrylate, hydroxyethyl acrylate and part of potassium persulfate aqueous solution into the reaction container in the step A at a constant speed under the stirring condition, preserving the temperature for 80min after completing dropwise adding, and dropwise adding the rest of sodium dodecyl sulfate aqueous solution into the reaction container in the step A when the temperature is preserved for 40 min; in the step, the feeding amount of butyl acrylate, methyl methacrylate and hydroxyethyl acrylate is respectively 15% of the total weight of the aqueous potassium persulfate solution, and the feeding amount of the aqueous potassium persulfate solution is 15% of the total weight of the aqueous potassium persulfate solution;
step C, a feeding stage: continuously heating the mixed solution obtained in the step B to 80 ℃, dropwise adding the rest butyl acrylate, methyl methacrylate, hydroxyethyl acrylate and the rest potassium persulfate aqueous solution into the reaction container in the step A at a constant speed under the stirring condition, continuously stirring in the dropwise adding process, and keeping the temperature unchanged;
step D, heat preservation reaction: c, continuously heating the mixed solution obtained in the step C to 85 ℃, preserving the temperature for 1h under the stirring condition, then performing cooling treatment, and discharging to obtain the hypoallergenic medical acrylate pressure-sensitive adhesive;
in steps A to D, the stirring speed was 300 rpm.
Example 17
The medical acrylate pressure-sensitive adhesive comprises the following raw materials in parts by weight: 78 parts of butyl acrylate, 22 parts of methyl methacrylate, 0.4 part of potassium persulfate, 2 parts of lauryl sodium sulfate, 0.1 part of sodium bicarbonate and 100 parts of deionized water;
the preparation method of the hypoallergenic medical acrylate pressure-sensitive adhesive comprises the following steps:
step A, preparation stage: adding part of sodium dodecyl sulfate and all sodium bicarbonate into a reaction vessel, adding part of deionized water, stirring and dissolving, heating to 65 ℃, and keeping the temperature for 40 min; wherein, the addition amount of the emulsifier is 25 percent of the total weight of the emulsifier;
step B, a seed stage: continuously heating the mixed solution obtained in the step A to 75 ℃, dropwise adding part of butyl acrylate, methyl methacrylate and part of potassium persulfate aqueous solution into the reaction container in the step A at a constant speed under the condition of stirring, preserving the temperature for 80min after finishing dropwise adding, and dropwise adding the rest of sodium dodecyl sulfate aqueous solution into the reaction container in the step A when the temperature preserving process is carried out for 40 min; in the step, the feeding amount of butyl acrylate and methyl methacrylate is respectively 15% of the total weight of the butyl acrylate and the methyl methacrylate, and the feeding amount of the potassium persulfate aqueous solution is 15% of the total weight of the potassium persulfate aqueous solution;
step C, a feeding stage: continuously heating the mixed solution obtained in the step B to 80 ℃, dropwise adding the rest butyl acrylate, the rest methyl methacrylate and the rest potassium persulfate aqueous solution into the reaction container in the step A at a constant speed under the stirring condition, continuously stirring in the dropwise adding process, and keeping the temperature unchanged;
step D, heat preservation reaction: c, continuously heating the mixed solution obtained in the step C to 85 ℃, preserving the temperature for 1h under the stirring condition, then performing cooling treatment, and discharging to obtain the hypoallergenic medical acrylate pressure-sensitive adhesive;
in steps A to D, the stirring speed was 300 rpm.
And (3) performance testing:
the medical acrylate pressure-sensitive adhesive prepared in the above examples 1 to 7 was subjected to a viscosity test, an initial adhesion test, a permanent adhesion test and a shear strength test in this order. Wherein the content of the first and second substances,
the viscosity test method comprises the following steps: the experiment was carried out using a DV-C digital display viscometer for viscosity measurement. Each medical acrylate pressure-sensitive adhesive was subjected to 3 parallel experiments, and the average value was taken as the final measurement value.
The initial adhesion test method comprises the following steps: the test was carried out according to GB/T33334-2016. Each medical acrylate pressure sensitive adhesive was subjected to 3 replicates and the average was the final measurement.
The permanent adhesion testing method comprises the following steps: the test was carried out according to GB/T4851-1998. Each medical acrylate pressure-sensitive adhesive was subjected to 3 parallel experiments, and the average value was taken as the final measurement value.
Tests show that the viscosity of the medical acrylate pressure-sensitive adhesive prepared in examples 1-17 is 206-4913 mpa · s, the permanent adhesion is 0.5 h-1.5 hmin, and the initial adhesion is 6-12 #, so that the medical acrylate pressure-sensitive adhesive meets the use requirements of children, old people and people with skin injury.
Meanwhile, the peel strength of the medical acrylate pressure-sensitive adhesive prepared in the above examples 1 to 17 is tested, specifically, the 180 ° peel strength test method is as follows: the test was carried out according to the GB/T2792-2004 standard. Each medical acrylate pressure sensitive adhesive was subjected to 3 parallel experiments, and the average value of the viscosity was taken as the final measurement value.
Tests prove that the 180-degree peel strength of the medical acrylate pressure-sensitive adhesive prepared in the embodiments 1-17 is 1N/cm-3.04N/cm, meets the standard of medical adhesive tapes, and has the characteristic of no residue after peeling in the using process.
In addition, the solid content and the conversion rate of the medical acrylate pressure-sensitive adhesive prepared in the above examples 1 to 17 were tested to evaluate the influence of sensitization.
The method for testing the solid content and the conversion rate comprises the following steps: the test is carried out by a gravimetric method. 1ml of emulsion to be tested is added into a culture dish with known weight, and the mixture is put into an oven with the temperature of 105 +/-1 ℃ for drying for 24 hours. The solid content and monomer conversion were calculated according to the formulas (1) and (2), respectively:
Figure RE-GDA0002571354890000181
conversion is actual solids/theoretical solids × 100% equation (2).
Tests prove that the medical acrylate pressure-sensitive adhesive prepared in examples 1-17 has the solid content of 48.66-50.5%, the conversion rate of 96.19-99.6%, high monomer conversion rate and low adhesive residual monomer content of the finished adhesive tape product; the adhesive tape is analyzed by combining the formula composition, the tackifying resin, the softening agent, the anti-aging agent, the thickening agent and the like contained in the current similar products sold in the market are not added in the formula of the adhesive tape, and the residual monomers are few, so that the irritation of the acrylate pressure-sensitive adhesive to the skin in use is effectively ensured to be greatly reduced, and the condition that infants and old people have contact dermatitis in MARSI (mark of illness) is improved.
In addition, the medical acrylate pressure-sensitive adhesive has the characteristics of no tackifying resin, softener, anti-aging agent and thickening agent, less residual monomers, and easy degradation of the structure of the polymer forming the main component of the medical acrylate pressure-sensitive adhesive, so the medical acrylate pressure-sensitive adhesive also has the characteristic of good biocompatibility.
The following table shows the test results of some of the examples.
Table 1:
example 3 Example 6 Example 7 Example 9 Example 11 Example 12
Solid content (%) 50.5 48.66 48.87 50.3 49.8 49.1
Conversion (%) 99.6 96.19 96.58 98.98 98.28 98.1
Viscosity (mpa.s) 3728 3722 4913 4912 206 2356
Permanent adhesive force (min) 48 59 37 58 60 81
Peel strength (N/cm) 1.7 1.2 1.15 2.69 1.86 1.05
Initial tack (#) 11 10 11 11 10 9
In the above examples, the functional monomers are added in examples 1, 4, 8, 10, 14, 15 and 16, and the functional monomers can be copolymerized with the soft monomers and the hard monomers to further improve the performance of the medical acrylate pressure-sensitive adhesive.
Compared with the embodiment without adding the functional monomer, the medical acrylate pressure-sensitive adhesive prepared by adding the functional monomer has no obvious change in the test values of solid content, conversion rate and particle size, the viscosity is obviously reduced, and meanwhile, the peel strength is improved. Wherein, for three alternative functional monomers of acrylic acid, hydroxyethyl acrylate and hydroxypropyl acrylate, the addition effect of the hydroxyethyl acrylate and the hydroxypropyl acrylate is better than that of the acrylic acid, and the addition effect of the hydroxyethyl acrylate is basically the same as that of the hydroxypropyl acrylate.
Specifically, in the above examples 1 to 17, the same preparation raw materials and amounts are used in examples 14 to 17, except that the functional monomers are added in examples 14 to 16: hydroxyethyl acrylate, and the addition amount of hydroxyethyl acrylate gradually increases.
The test results are shown in table 2 below.
Table 2:
and (3) testing items: example 14 Example 15 Example 16 Example 17
Viscosity (mpa.s) 1632 1764 594 4320
Peel strength (N/cm) 1.73 3.04 1.53 1.05
As can be seen from the test results in table 1 above, compared with the embodiment without adding the functional monomer, the addition of a small amount of the functional monomer can significantly reduce the viscosity of the pressure-sensitive adhesive, which is beneficial to improving the comfort level of the adhesion between the pressure-sensitive adhesive and the skin; meanwhile, the peel strength of the pressure-sensitive adhesive is further improved to more than 50%, so that the pressure-sensitive adhesive is free from residue after being peeled, and is better suitable for children, old people and patients with skin injury and the market demand.
It should be noted that the above embodiments are only used for illustrating the technical solutions of the present invention and are not limited. Although the present invention has been described in detail with reference to the preferred embodiments, it will be understood by those skilled in the art that various changes may be made and equivalents may be substituted without departing from the scope of the present invention.

Claims (10)

1. The low-sensitization medical acrylate pressure-sensitive adhesive is characterized by comprising 75-90 parts by weight of soft monomers, 10-25 parts by weight of hard monomers, 0.2-0.7 part by weight of initiators, 1-3 parts by weight of emulsifiers, 0.1-0.2 part by weight of buffers and 100-110 parts by weight of deionized water; wherein the soft monomer is an acrylate substance prepared by the reaction of acrylic acid and alcohol with 4-8 carbon atoms; the hard monomer is methyl methacrylate, methyl acrylate, vinyl acetate, styrene, acrylonitrile or acrylamide.
2. The hypoallergenic medical acrylate pressure-sensitive adhesive according to claim 1, wherein the soft monomer is at least one of butyl acrylate and isooctyl acrylate.
3. The hypoallergenic medical acrylate pressure-sensitive adhesive according to claim 2, characterized in that the soft monomer is butyl acrylate and the hard monomer is methyl methacrylate.
4. The hypoallergenic medical acrylate pressure-sensitive adhesive according to claim 1, characterized by further comprising 3-7 parts of functional monomers; the functional monomer is acrylic acid, hydroxyethyl acrylate or hydroxypropyl acrylate.
5. The hypoallergenic medical acrylate pressure-sensitive adhesive according to claim 4, characterized in that the functional monomer is hydroxyethyl acrylate.
6. The hypoallergenic medical acrylate pressure-sensitive adhesive according to claim 1, characterized in that the initiator is potassium persulfate or ammonium persulfate.
7. The hypoallergenic medical acrylate pressure-sensitive adhesive according to claim 1, characterized in that the emulsifier is sodium dodecyl sulfate.
8. The hypoallergenic medical acrylate pressure-sensitive adhesive according to claim 1, wherein the buffer is a carbonate or a phosphate.
9. The preparation method of the hypoallergenic medical acrylate pressure-sensitive adhesive according to any one of claims 1 to 8, characterized by comprising the following steps:
step A, preparation stage: adding part of the emulsifier and all the buffering agent into a reaction container, adding part of deionized water, stirring and dissolving, heating to 55-65 ℃, and keeping the temperature for 30-40 min; wherein the addition amount of the emulsifier is 10-30% of the total weight of the emulsifier;
step B, a seed stage: continuously heating the mixed solution obtained in the step A to 65-75 ℃, dropwise adding the seed monomer and the initiator aqueous solution into the reaction container in the step A at a constant speed under the stirring condition, preserving the temperature for 50-90 min after dropwise adding, and dropwise adding the residual emulsifier aqueous solution into the reaction container in the step A when the temperature is preserved for 25-45 min; wherein the feeding amount of the seed monomer is 5-20% of the total weight of the mixed monomer; the feeding amount of the initiator is 5-20% of the total weight of the initiator;
step C, a feeding stage: continuously heating the mixed solution obtained in the step B to 75-80 ℃, dropwise adding the residual initiator aqueous solution and the residual mixed monomer into the reaction container in the step A at a constant speed under the stirring condition, and keeping the temperature unchanged in the dropwise adding process;
step D, heat preservation reaction: and C, continuously heating the mixed solution obtained in the step C to 80-85 ℃, preserving the heat for 1-1.5 hours under the stirring condition, then cooling, and discharging.
10. The method for preparing the hypoallergenic medical acrylate pressure-sensitive adhesive according to claim 9, wherein in the steps a to D, the stirring speed is 250 to 400 rpm.
CN202010467329.4A 2020-05-28 2020-05-28 Low-sensitization medical acrylate pressure-sensitive adhesive and preparation method thereof Pending CN111534256A (en)

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CN112915250A (en) * 2021-01-29 2021-06-08 振德医疗用品股份有限公司 Low-viscosity isolation acrylic pressure-sensitive adhesive for wound surface and preparation method thereof
CN114940881A (en) * 2022-06-30 2022-08-26 浙江冠豪新材料有限公司 High-solid low-viscosity pressure-sensitive adhesive for anilox roller
CN116904149A (en) * 2023-09-12 2023-10-20 潍坊胜达科技股份有限公司 Water-based pressure-sensitive adhesive for low-tackifying protective film and preparation method thereof

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EP1297033B1 (en) * 2000-06-23 2005-03-30 Solutia Inc. Process for forming solid pressure sensitive adhesive polymer microspheres
CN101434819A (en) * 2008-12-10 2009-05-20 广东恒大新材料科技有限公司 Aqueous adhesive for binding rubber and metal and preparation thereof
CN110551246A (en) * 2018-06-04 2019-12-10 阜阳师范学院 Acrylate emulsion and preparation method thereof
CN110551245A (en) * 2018-06-04 2019-12-10 阜阳师范学院 Core-shell emulsion and preparation method thereof

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EP1297033B1 (en) * 2000-06-23 2005-03-30 Solutia Inc. Process for forming solid pressure sensitive adhesive polymer microspheres
CN101434819A (en) * 2008-12-10 2009-05-20 广东恒大新材料科技有限公司 Aqueous adhesive for binding rubber and metal and preparation thereof
CN110551246A (en) * 2018-06-04 2019-12-10 阜阳师范学院 Acrylate emulsion and preparation method thereof
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Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN112915250A (en) * 2021-01-29 2021-06-08 振德医疗用品股份有限公司 Low-viscosity isolation acrylic pressure-sensitive adhesive for wound surface and preparation method thereof
CN114940881A (en) * 2022-06-30 2022-08-26 浙江冠豪新材料有限公司 High-solid low-viscosity pressure-sensitive adhesive for anilox roller
CN116904149A (en) * 2023-09-12 2023-10-20 潍坊胜达科技股份有限公司 Water-based pressure-sensitive adhesive for low-tackifying protective film and preparation method thereof

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