CN112625172A

CN112625172A - Fluorine-free polymer and preparation method and application thereof

Info

Publication number: CN112625172A
Application number: CN202011623840.5A
Authority: CN
Inventors: 曹步军
Original assignee: Chengdu Sage Stone Technology Co ltd
Current assignee: Chengdu Youshitong New Material Technology Co ltd
Priority date: 2020-12-31
Filing date: 2020-12-31
Publication date: 2021-04-09
Anticipated expiration: 2040-12-31
Also published as: CN112625172B

Abstract

The invention belongs to the technical field of functional materials, and particularly discloses a fluorine-free polymer and application thereof. The invention forms a new fluorine-free polymer through the polymerization reaction of three or more types of monomers of the component (A), the component (B) and the component (C), and the fluorine-free polymer also has good film-forming property on porous fiber materials of paper. Compared with a single type of polymer, the fluorine-free polymer can obviously reduce the surface energy of a base material after forming a film, and has excellent water and oil resistance. The raw materials selected by the invention do not contain fluorine, are safe and environment-friendly, do not have leaching, can be used for food packaging paper, and solve the problem that most of the existing packaging paper uses fluorine-containing oil-proof agents; the invention has low cost of raw materials and small using amount, and does not increase the production cost of the oil-proof packaging paper.

Description

Fluorine-free polymer and preparation method and application thereof

Technical Field

The invention relates to the technical field of polymer synthesis and application, in particular to a fluorine-free polymer and a preparation method and application thereof.

Background

The waterproof and oil-proof packaging material is indispensable in human life, but the commonly used waterproof and oil-proof packaging materials in the market are often polypropylene, polypropylene resin, polyethylene and the like, and according to incomplete statistics, the number of plastic snack boxes consumed in China every year exceeds 300 hundred million. However, these plastic packaging materials are often difficult to handle after use, causing significant damage to the human environment. Therefore, how to replace the packaging materials which are difficult to degrade becomes a focus of attention.

The paper material is a common packaging material in daily life, can be recycled and is easy to degrade, so that the damage to the environment is less, the material is easy to obtain, the price is moderate, and the paper material is easy to accept by consumers. However, since the paper material itself does not have oil and water resistance, the application field thereof is greatly limited. The paper material is subjected to necessary water-proof and oil-proof treatment, so that the paper material can become an excellent substitute for the plastic packaging material.

At present, the oil-proof treatment of paper materials is mainly divided into two types, the first type is to coat oil-proof plastics on the surface of paper, and the method can only reduce the pollution of the plastics but cannot radically treat the pollution of the plastics. The second is to add chemical agent for oil-proof into the paper pulp or to coat chemical agent for oil-proof on the paper surface, so as to achieve the effect of water-proof and oil-proof. The method greatly retains the advantages of paper biodegradation and recycling.

At present, chemical oil-proof agents added or coated on paper pulp are mainly divided into fluorine-containing oil-proof agents and fluorine-free oil-proof agents, and the fluorine-containing oil-proof agents are mainly perfluoroalkyl compounds and have excellent hydrophobic and oleophobic properties. However, the fluorine-containing oil-proof agent has the environmental pollution problem and the health problem of organisms are increasingly attracted, so that the fluorine-free oil-proof agent has the interest of people along with the environmental protection trend, the fluorine-free oil-proof agent is not easy to enrich in the organisms, is easy to degrade, is harmless to the human bodies, is a safer and more environment-friendly product, and now the ecological environment protection is increasingly attracted by people, the concept of the fluorine-free oil-proof agent is more easily accepted by the public, so that the fluorine-free oil-proof agent has huge market potential and is a hotspot of current research.

The development of the fluorine-free oil-proof agent is much later than that of the fluorine-containing oil-proof agent, the application of the degradable high polymer material in the field of packaging paper is more and more extensive, particularly for food packaging, the raw materials are pollution-free and degradable, the body health of consumers and the sustainable development of the environment are ensured, and polysaccharide polymers, paraffin, beeswax and the like used as the oil-proof agent and artificially synthesized acrylate copolymers are used. However, natural polymer materials such as dispersed whey protein, zein, isolated soy protein, chitosan and the like generally have high viscosity and are not beneficial to industrial production; the cost is high; the oil resistance level is not high; high temperature difference resistance and the like. The conventional acrylate polymer also has the problems of poor oil resistance, easy water absorption and swelling, adhesion and the like.

Disclosure of Invention

In order to solve the problems in the background art, the present invention provides a fluorine-free polymer, a preparation method and an application thereof.

In a first aspect, the present invention provides a fluorine-free polymer.

A fluorine-free polymer is mainly copolymerized by the following monomers:

component (A) acrylonitrile monomer;

component (B) has one or more short chain acrylate monomers as shown in formula 1:

CH₂(= O) -O-Y of formula 1

In the general formula 1, X is a hydrogen atom, a substituted or unsubstituted alkyl group having 1 to 10 carbon atoms or a halogen atom other than a fluorine atom, and Y is a substituted or unsubstituted alkyl group having 1 to 10 carbon atoms or a substituted or unsubstituted cyclic alkyl group having 3 to 10 carbon atoms; and

component (C) is a vinyl aromatic monomer and/or an olefinic monomer.

Wherein the component (B) is selected from any one or more of methyl acrylate, ethyl acrylate, butyl acrylate, methyl methacrylate, ethyl methacrylate, butyl methacrylate, cyclohexyl acrylate, 2-ethylhexyl acrylate, cyclohexyl methacrylate and 2-ethylhexyl methacrylate.

The vinyl aromatic monomer in the component (C) is any one of styrene, 1-methyl vinyl benzene and divinylbenzene; the olefin monomer is selected from any one of ethylene, vinyl acetate, propylene, 1-butylene and butadiene.

In the invention, the glass transition temperature of the fluorine-free polymer is-30-40 ℃.

The weight average molecular weight of the fluorine-free polymer is 20-70 ten thousand.

The component (A) accounts for 30-60 wt% of the total weight of the fluorine-free polymer monomer.

The weight ratio of the component (A), the component (B) and the component (C) is 1: 0.5-1.2: 0.3-0.8.

In a specific embodiment, the fluorine-free polymer may further comprise a polysaccharide high molecular material; the polysaccharide high molecular material comprises but is not limited to sodium alginate, chitosan and acetylated starch; the addition amount of the polysaccharide polymer material can be regulated and controlled according to different types. For example, the addition ratio of the fluorine-free polymer to the sodium alginate can be 1: 0.005-0.05; the addition ratio of the fluorine-free polymer to the chitosan can be 1: 0.001-0.005; the addition ratio of the fluorine-free polymer to the acetylated starch can be 1: 0.005-0.03.

In a second aspect, the present invention also provides a process for preparing said fluorine-free polymer of the first invention of the present invention.

The method for preparing the fluorine-free polymer is a reaction of a component (A), a component (B) and a component (C) in the presence of an emulsifier, an initiator and water, and specifically comprises the following steps:

uniformly mixing the component (A), the component (B) and the component (C) for first emulsification to obtain a first emulsion; and

carrying out second emulsification on the first emulsion and carrying out polymerization reaction;

wherein the total weight of component (A), component (B) and component (C) is 18-70% of the total weight of the fluorine-free polymer; the ratio of the addition amount of the emulsifier to the total weight of the component (A), the component (B) and the component (C) is 1: 0.05 to 0.2; the ratio of the addition amount of the initiator to the total weight of the component (A), the component (B) and the component (C) is 1: 0.02-0.05; the balance being water.

In the present invention, the emulsifier comprises an anionic emulsifier and/or a nonionic emulsifier; wherein the anionic emulsifier is any one or more of sodium dodecyl sulfate, sodium dodecyl alcohol polyoxyethylene ether sulfate or ammonium alkyl phenol ethoxylate sulfate; the non-ionic emulsifier is selected from one or more of polyoxyethylene sorbitan fatty acid ester, sugar ester, polyether surfactant, acetylene glycol surfactant, polyethylene glycol, polypropylene glycol, ethoxylated castor oil, oleic acid ethoxylate, alkylphenol ethoxylate, and copolymer of organosilicon and polyether.

The initiator is one or more of ammonium persulfate, potassium persulfate and sodium thiosulfate.

In one embodiment, the method further comprises:

dividing the emulsifier into a first weight part and a second weight part, wherein the first weight part is 50-80% of the total weight of the emulsifier, and the balance is the second weight part;

dividing the water into a third weight part and a fourth weight part, wherein the third weight part is 50% of the total weight of the water, and the balance is the fourth weight part;

dividing the initiator into a fifth weight part and a sixth weight part, wherein the fifth weight part is 8-15% of the total weight of the initiator, and the balance is the sixth weight part; and

the first emulsion is divided into a seventh weight portion and an eighth weight portion, wherein the seventh weight portion is 10-20% of the total weight of the first emulsion, and the balance is eight weight portions.

Furthermore, the first emulsification method specifically comprises the following steps:

uniformly stirring the first weight part of emulsifier and the third weight part of water, adding the component (A), the component (B) and the component (C), uniformly mixing, and emulsifying for 0.5-1.0 h.

The second emulsification of the first emulsion and the polymerization reaction comprise first polymerization and second polymerization, and specifically comprise the following steps:

uniformly mixing the emulsifier with the second weight part and the water with the fourth weight part, stirring for 0.5-1.0 h, heating to 60-80 ℃, adding the first emulsion with the seventh weight part and the initiator with the fifth weight part, heating to 80-90 ℃, reacting for 0.5-1.0 h, and finishing the first polymerization when the emulsion turns blue; and

and adding the eighth part by weight of the first emulsion and the sixth part by weight of the initiator after the first polymerization is completed, controlling the adding time to be 2.0-6.0 h, raising the temperature to 85-95 ℃ after the addition is completed, continuing to perform heat preservation reaction for 1-2 h, and then reducing the temperature to 30-40 ℃ to complete the second polymerization.

In a third aspect, the invention also provides an oil-proofing agent.

An oil-repellent agent comprising a fluorine-free polymer, a liquid medium containing water and an auxiliary agent; wherein the fluorine-free polymer is mainly copolymerized by the following monomers:

component (A) acrylonitrile monomer;

CH₂(= O) -O-Y of formula 1

component (C) is a vinyl aromatic monomer and/or an olefinic monomer.

The glass transition temperature of the fluorine-free polymer is-30 to 40 ℃; the weight average molecular weight of the fluorine-free polymer is 20-70 ten thousand; the component (A) accounts for 30-60 wt% of the total weight of the fluorine-free polymer monomer; the weight ratio of the component (A), the component (B) and the component (C) is 1: 0.5-1.2: 0.3-0.8.

The auxiliaries include, but are not limited to, any one or more of surfactants, rheology modifiers, defoamers, preservatives, matting agents, and pH adjusters.

In another embodiment, the fluorine-free polymer further comprises a polysaccharide high molecular material; the polysaccharide high molecular material comprises but is not limited to sodium alginate, chitosan and acetylated starch.

In a fourth aspect, the present invention also provides a paper product treated with the oil-repellent agent of the third aspect of the present invention.

In a fifth aspect, the present invention also provides the use of a fluorine-free polymer.

Use of a fluorine-free polymer in the oil-repellent component of a paper packaging material for food products, said fluorine-free polymer being formed essentially of a copolymerisation of:

component (A) acrylonitrile monomer;

CH₂(= O) -O-Y of formula 1

component (C) is a vinyl aromatic monomer and/or an olefinic monomer.

The vinyl aromatic monomer in the component (C) is selected from any one of styrene, 1-methyl vinyl benzene and divinylbenzene, and the olefin monomer is selected from any one of ethylene, vinyl acetate, propylene, 1-butylene and butadiene.

The glass transition temperature of the fluorine-free polymer is-30 to 40 ℃; the weight average molecular weight of the fluorine-free polymer is 20-70 ten thousand; the component (A) accounts for 30-60 wt% of the total weight of the fluorine-free polymer monomer.

The use according to any one of claims 34 to 36, wherein the weight ratio of component (a), component (B) and component (C) is from 1:0.5 to 1.2:0.3 to 0.8.

In another embodiment, the fluorine-free polymer further comprises a polysaccharide high molecular material, including but not limited to sodium alginate, chitosan, acetylated starch.

Compared with the prior art, the invention has the following beneficial effects:

the invention forms a new fluorine-free polymer through the polymerization reaction of three or more types of monomers of the component (A), the component (B) and the component (C), and the fluorine-free polymer also has good film-forming property on porous fiber materials such as paper. Compared with a single type of polymer, the fluorine-free polymer disclosed by the invention has very high surface energy to water and oil after being formed into a film, and has excellent water and oil resistance.

The fluorine-free polymer can be compounded with polysaccharide high molecular materials, and the polysaccharide high molecular materials have good film forming performance and good environmental compatibility, so that the film forming performance of the product can be improved, the raw material consumption can be reduced, and the environmental protection performance of the product is better.

The fluorine-free polymer is compounded into an oil-proof agent and then coated on the surface of a paper product, and the obtained paper product has a good oil-proof effect and can achieve an effect of adjustable gloss.

The fluorine-free polymer is applied as an oil-proof component of the food paper packaging material, so that the food packaging material also has good anti-blocking property.

The raw materials selected by the invention do not contain fluorine, are safe and environment-friendly, do not have leaching, can be used for food packaging paper, and solve the problem that most of the existing packaging paper uses fluorine-containing fluorine-free polymers; the invention has low cost of raw materials and small using amount, and does not increase the production cost of the oil-proof packaging paper.

Drawings

FIGS. 1 to 2 are graphs showing the effect of the anti-blocking test on each sample in example 24;

FIG. 3 is a LC-MS spectrum of a sample under several different treatment methods in Experimental example 2.

Detailed Description

The following description of the embodiments of the present invention will be made with reference to the accompanying drawings. It should be noted that the description of the embodiments is provided to help understanding of the present invention, but the present invention is not limited thereto. In addition, the technical features involved in the embodiments of the present invention described below may be combined with each other as long as they do not conflict with each other.

The unit of the addition amount of each substance in the examples of the present invention and the comparative examples is g, which represents the addition amount of each component required per 100g of the finished product.

Example 1

Synthesis of fluorine-free Polymer Y1:

adding 0.6g of polyoxyethylene sorbitan fatty acid ester and 40g of deionized water into an emulsification reaction kettle, uniformly stirring, adding 10g of acrylonitrile monomer, 5g of methyl acrylate monomer and 3g of styrene monomer, and emulsifying for 0.5h to obtain a first emulsion;

adding 40g of deionized water and 0.6g of polyoxyethylene sorbitan fatty acid ester into a reaction kettle, stirring for 0.5h, heating to 60 ℃, adding 20% of the total weight of the first emulsion, simultaneously adding 0.1g of initiator ammonium persulfate, heating to 90 ℃, reacting for 0.5h, slowly adding the remaining first emulsion and 0.7g of ammonium persulfate when the emulsion turns blue, controlling the adding time to be 2h, heating to 85 ℃ after the addition is finished, continuing the heat preservation reaction for 1h, then cooling to 40 ℃, detecting the vitrification temperature and the weight average molecular weight of reactants after filtering, and determining that the indexes meet the requirements to obtain the fluorine-free polymer product.

Example 2

Synthesis of fluorine-free Polymer Y2:

adding 1.6g of emulsifier fatty alcohol-polyoxyethylene ether and 35.5g of deionized water into an emulsification reaction kettle, uniformly stirring, adding 10g of acrylonitrile monomer, 8g of ethyl acrylate monomer and 8g of styrene monomer, and emulsifying for 0.5h to obtain a first emulsion;

adding 35.5g of deionized water and 0.4g of fatty alcohol-polyoxyethylene ether into a reaction kettle, stirring for 0.5h, heating to 60 ℃, adding 20% of the total weight of the first emulsion, simultaneously adding 0.1g of initiator ammonium persulfate, heating to 90 ℃, reacting for 0.5h, slowly remaining the first emulsion and 0.9g of ammonium persulfate when the emulsion turns blue, controlling the adding time to be 3h, heating to 95 ℃ after the addition is finished, continuing to perform heat preservation reaction for 1h, then cooling to 30 ℃, detecting the glass transition temperature and the weight average molecular weight of reactants after filtering, and determining that the indexes meet the requirements to obtain the fluorine-free polymer product.

Example 3

Synthesis of fluorine-free Polymer Y3:

adding 1.6g of ethoxylated castor oil and 34.5g of deionized water into an emulsion reaction kettle, uniformly stirring, adding 10g of acrylonitrile monomer, 10g of butyl acrylate monomer, 5g of styrene monomer and 3g of ethylene monomer, and emulsifying for 1.0h to obtain a first emulsion;

adding 34.5g of deionized water and 0.4g of sodium dodecyl sulfate into a reaction kettle, stirring for 0.5h, heating to 60 ℃, adding 18% of the total weight of the first emulsion, simultaneously adding 0.1g of initiator ammonium persulfate, heating to 90 ℃, reacting for 0.5h, controlling the adding time of the first emulsion and 0.9g of ammonium persulfate which are slowly remained when the emulsion turns blue, heating to 95 ℃ after the addition is finished, continuing to perform heat preservation reaction for 1h, then cooling to 30 ℃, detecting the glass transition temperature and the weight average molecular weight of reactants after filtering, and determining that the indexes meet the requirements to obtain the fluorine-free polymer product.

Example 4

Synthesis of fluorine-free Polymer Y4:

adding 1.0g of lauryl alcohol polyoxyethylene ether sodium sulfate and 37.5g of deionized water into an emulsion reaction kettle, uniformly stirring, adding 10g of acrylonitrile monomer, 10g of methyl methacrylate monomer and 3g of propylene monomer, and emulsifying for 1.0h to obtain a first emulsion;

adding 37.5g of deionized water and 0.5g of lauryl alcohol polyoxyethylene ether sodium sulfate into a reaction kettle, stirring for 0.5h, heating to 70 ℃, adding 18% of the total weight of the first emulsion, simultaneously adding 0.05g of initiator ammonium persulfate, heating to 90 ℃, reacting for 0.5h, slowly remaining the first emulsion and 0.45g of ammonium persulfate when the emulsion turns blue, controlling the adding time to be 2.5h, heating to 90 ℃ after the addition is finished, continuing to perform heat preservation reaction for 1h, then cooling to 35 ℃, detecting the vitrification temperature and the weight average molecular weight of reactants after filtering, and determining that the indexes meet the requirements to obtain the fluorine-free polymer product.

Example 5

Synthesis of fluorine-free Polymer Y5:

adding 1g of emulsifier alkyl alkynediol polyether and 33.5g of deionized water into an emulsification reaction kettle, uniformly stirring, adding 10g of acrylonitrile monomer, 12g of ethyl methacrylate monomer and 5g of vinyl acetate monomer, and emulsifying for 1.0h to obtain a first emulsion;

adding 40.5g of deionized water and 1g of polyethylene glycol into a reaction kettle, stirring for 0.5h, heating to 70 ℃, adding 15% of the total weight of the first emulsion, simultaneously adding 0.1g of initiator ammonium persulfate, heating to 90 ℃, reacting for 0.5h, slowly adding the remaining first emulsion and 0.9g of ammonium persulfate when the emulsion turns blue, controlling the adding time to be 2.5h, heating to 87 ℃ after the addition is finished, continuing to carry out heat preservation reaction for 1h, then cooling to 38 ℃, detecting the vitrification temperature and the weight average molecular weight of reactants after filtering, and determining that the indexes meet the requirements to obtain the fluorine-free polymer product.

Example 6

Synthesis of fluorine-free Polymer Y6:

adding 1.8g of emulsifier oleic acid ethoxylate and 31.5g of deionized water into an emulsification reaction kettle, uniformly stirring, adding 10g of acrylonitrile monomer, 10g of butyl acrylate monomer, 2g of methyl methacrylate, 3g of 1-methylvinylbenzene and 5g of 1-butylene monomer, and emulsifying for 1.0h to obtain a first emulsion;

adding 34.5g of deionized water and 1g of oleic acid ethoxylate into a reaction kettle, stirring for 0.5h, heating to 70 ℃, adding 17% of the total weight of the first emulsion, simultaneously adding 0.12g of initiator ammonium persulfate, heating to 90 ℃, reacting for 0.5h, slowly adding the remaining first emulsion and 1.53g of ammonium persulfate when the emulsion turns blue, controlling the adding time to be 2.1h, heating to 87 ℃ after the addition is finished, continuing the heat preservation reaction for 1h, then cooling to 36 ℃, detecting the vitrification temperature and the weight average molecular weight of reactants after filtering, and determining that the indexes meet the requirements to obtain the fluorine-free polymer product.

Example 7

Synthesis of fluorine-free Polymer Y7:

adding 2g of emulsifier alkylphenol ethoxylate and 31.5g of deionized water into an emulsification reaction kettle, uniformly stirring, adding 15g of acrylonitrile monomer, 8g of cyclohexyl acrylate and 10g of butadiene monomer, and emulsifying for 1.0h to obtain a first emulsion;

adding 31.5g of deionized water and 0.6g of a copolymer of organic silicon and polyether into a reaction kettle, stirring for 1h, heating to 70 ℃, adding 16% of the total weight of the first emulsion, simultaneously adding 0.14g of an initiator potassium persulfate, heating to 80 ℃, reacting for 0.5h, slowly remaining the first emulsion and 1.26g of potassium persulfate when the emulsion turns blue, controlling the adding time to be 3.5h, heating to 90 ℃ after the addition is finished, continuing to perform heat preservation reaction for 2h, then cooling to 39 ℃, detecting the vitrification temperature and the weight average molecular weight of reactants after filtering, and determining that the indexes meet the requirements to obtain the fluorine-free polymer product.

Example 8

Synthesis of fluorine-free Polymer Y8:

adding 1.3g of emulsifier alkyl alkynediol polyether and 29.5g of deionized water into an emulsification reaction kettle, uniformly stirring, adding 15g of acrylonitrile monomer, 10g of acrylic acid-2-ethylhexyl ester and 12g of vinyl acetate monomer, and emulsifying for 1.0h to obtain a first emulsion;

adding 29.5g of deionized water and 1.3g of polyethylene glycol into a reaction kettle, stirring for 1h, heating to 70 ℃, adding 10% of the total weight of the first emulsion, simultaneously adding 0.14g of initiator potassium persulfate, heating to 80 ℃, reacting for 0.5h, slowly adding the remaining first emulsion and 1.26g of potassium persulfate when the emulsion turns blue, controlling the adding time to be 3h, heating to 90 ℃ after the addition is finished, continuing to carry out heat preservation reaction for 2h, then cooling to 40 ℃, detecting the vitrification temperature and the weight average molecular weight of reactants after filtering, and determining that the indexes meet the requirements to obtain the fluorine-free polymer product.

Example 9

Synthesis of fluorine-free Polymer Y9:

adding 2.4g of emulsifier ethoxylated castor oil and 29g of deionized water into an emulsification reaction kettle, uniformly stirring, adding 15g of acrylonitrile monomer, 10g of cyclohexyl methacrylate, 6g of ethylene monomer and 6g of 1-methyl vinyl benzene, and emulsifying for 1.0h to obtain a first emulsion;

adding 29g of deionized water and 1g of sodium dodecyl sulfate into a reaction kettle, stirring for 1h, heating to 70 ℃, adding 10% of the total weight of the first emulsion, simultaneously adding 0.14g of potassium persulfate as an initiator, heating to 80 ℃, reacting for 0.5h, slowly adding the remaining first emulsion and 1.26g of potassium persulfate when the emulsion turns blue, controlling the adding time to be 4h, heating to 90 ℃ after the addition is finished, continuing to perform heat preservation reaction for 2h, then cooling to 30 ℃, detecting the vitrification temperature and the weight average molecular weight of reactants after filtering, and determining that the indexes meet the requirements to obtain the fluorine-free polymer product.

Example 10

Synthesis of fluorine-free Polymer Y10:

adding 2.4g of emulsifier polyoxyethylene sorbitan fatty acid ester and 26.5g of deionized water into an emulsification reaction kettle, uniformly stirring, adding 15g of acrylonitrile monomer, 15g of 2-ethylhexyl methacrylate, 2g of divinylbenzene and 10g of ethylene monomer, and emulsifying for 1.0h to obtain a first emulsion;

adding 26.5g of deionized water and 1g of polypropylene glycol into a reaction kettle, stirring for 1h, heating to 70 ℃, adding 12% of the total weight of the first emulsion, simultaneously adding 0.14g of initiator potassium persulfate, heating to 80 ℃, reacting for 0.5h, slowly adding the remaining first emulsion and 1.26g of potassium persulfate when the emulsion turns blue, controlling the adding time to be 3.7h, heating to 90 ℃ after the addition is finished, continuing to carry out heat preservation reaction for 2h, then cooling to 38 ℃, detecting the vitrification temperature and the weight average molecular weight of reactants after filtering, and determining that the indexes meet the requirements to obtain the fluorine-free polymer product.

Example 11

Synthesis of fluorine-free Polymer Y11:

adding 3g of emulsifier alkylphenol ethoxylate and 25.5g of deionized water into an emulsification reaction kettle, uniformly stirring, adding 15g of acrylonitrile monomer, 10g of methyl acrylate, 8g of 2-ethylhexyl methacrylate and 10g of styrene, and emulsifying for 1.0h to obtain a first emulsion;

adding 25.5g of deionized water and 1.2g of alkylphenol ethoxylate into a reaction kettle, stirring for 1h, heating to 70 ℃, adding 14% of the total weight of the first emulsion, simultaneously adding 0.14g of initiator potassium persulfate, heating to 80 ℃, reacting for 0.5h, slowly remaining first emulsion and 1.26g of potassium persulfate when the emulsion turns blue, controlling the adding time to be 3h, heating to 90 ℃ after the addition is finished, continuing to perform heat preservation reaction for 2h, then cooling to 30 ℃, detecting the vitrification temperature and the weight average molecular weight of reactants after filtering, and determining that the indexes meet the requirements to obtain the fluorine-free polymer product.

Example 12

Synthesis of fluorine-free Polymer Y12:

adding 3.3g of emulsifier fatty alcohol polyether and 25.5g of deionized water into an emulsification reaction kettle, uniformly stirring, adding 15g of acrylonitrile monomer, 10g of methyl methacrylate, 8g of acrylic acid-2-ethylhexyl ester and 10g of vinyl acetate, and emulsifying for 1.0h to obtain a first emulsion;

adding 25.5g of deionized water and 0.9g of fatty acid sugar ester into a reaction kettle, stirring for 1h, heating to 70 ℃, adding 13% of the total weight of the first emulsion, simultaneously adding 0.14g of initiator potassium persulfate, heating to 80 ℃, reacting for 0.5h, slowly remaining first emulsion and 1.26g of potassium persulfate when the emulsion turns blue, controlling the adding time to be 4h, heating to 90 ℃ after the addition is finished, continuing to perform heat preservation reaction for 2h, then cooling to 40 ℃, detecting the vitrification temperature and the weight average molecular weight of reactants after filtering, and determining that the indexes meet the requirements to obtain the fluorine-free polymer product.

Example 13

Synthesis of fluorine-free Polymer Y13:

adding 3g of emulsifier ethoxylated castor oil and 26g of deionized water into an emulsification reaction kettle, uniformly stirring, adding 20g of acrylonitrile monomer, 10g of cyclohexyl methacrylate, 10g of styrene and 4g of ethylene monomer, and emulsifying for 1.0h to obtain a first emulsion;

adding 26g of deionized water and 3g of sodium lauryl alcohol polyoxyethylene ether sulfate into a reaction kettle, stirring for 1h, heating to 80 ℃, adding 15% of the total weight of the first emulsion, simultaneously adding 0.16g of initiator sodium thiosulfate, heating to 90 ℃, reacting for 1h, slowly adding the remaining first emulsion and 1.84g of sodium thiosulfate when the emulsion turns blue, controlling the adding time to be 5.5h, heating to 95 ℃ after the addition is finished, continuing to perform heat preservation reaction for 1.5h, then cooling to 35 ℃, detecting the glass transition temperature and the weight average molecular weight of reactants after filtering, and determining that the indexes meet the requirements to obtain the fluorine-free polymer product.

Example 14

Synthesis of fluorine-free Polymer Y14:

adding 2.5g of emulsifier alkylphenol ethoxylate and 27g of deionized water into an emulsification reaction kettle, uniformly stirring, adding 20g of acrylonitrile monomer, 10g of cyclohexyl methacrylate and 10g of butadiene, and emulsifying for 1.0h to obtain a first emulsion;

adding 27g of deionized water and 2g of alkylphenol ethoxylate into a reaction kettle, stirring for 1h, heating to 80 ℃, adding 15% of the total weight of the first emulsion, simultaneously adding 0.15g of initiator sodium thiosulfate, heating to 90 ℃, reacting for 1h, slowly adding the remaining first emulsion and 1.35g of sodium thiosulfate when the emulsion turns blue, controlling the adding time to be 6h, heating to 95 ℃ after the addition is finished, continuing to perform heat preservation reaction for 1.5h, then cooling to 40 ℃, detecting the vitrification temperature and the weight average molecular weight of reactants after filtering, and determining that the indexes meet the requirements to obtain the fluorine-free polymer product.

Example 15

Synthesis of fluorine-free Polymer Y15:

adding 4g of emulsifier oleic acid ethoxylate and 23g of deionized water into an emulsification reaction kettle, uniformly stirring, adding 20g of acrylonitrile monomer, 10g of butyl methacrylate, 2g of styrene and 14g of ethylene monomer, and emulsifying for 1.0h to obtain a first emulsion;

adding 23g of deionized water and 2g of polyoxyethylene sorbitan fatty acid ester into a reaction kettle, stirring for 1h, heating to 80 ℃, adding 10% of the total weight of the first emulsion, simultaneously adding 0.3g of initiator sodium thiosulfate, heating to 90 ℃, reacting for 1h, slowly adding the remaining first emulsion and 1.7g of sodium thiosulfate when the emulsion turns blue, controlling the adding time to be 5.2h, heating to 95 ℃ after the addition is finished, continuing to perform heat preservation reaction for 1.5h, then cooling to 39 ℃, filtering, detecting the glass transition temperature and the weight average molecular weight of reactants, and determining that the indexes meet the requirements to obtain the fluorine-free polymer product.

Example 16

Synthesis of fluorine-free Polymer Y16:

adding 3g of emulsifier ethoxylated castor oil and 24g of deionized water into an emulsification reaction kettle, uniformly stirring and adding 20g of acrylonitrile monomer, 10g of acrylic acid-2-ethylhexyl ester, 8g of 1-methyl vinyl benzene and 8g of 1-butylene, and emulsifying for 1.0h to obtain a first emulsion;

adding 24g of deionized water and 1.5g of polypropylene glycol into a reaction kettle, stirring for 1h, heating to 80 ℃, adding 16% of the total weight of the first emulsion, simultaneously adding 0.15g of initiator sodium thiosulfate, heating to 90 ℃, reacting for 1h, slowly adding the remaining first emulsion and 1.35g of sodium thiosulfate when the emulsion turns blue, controlling the adding time to be 5h, heating to 95 ℃ after the addition is finished, continuing to perform heat preservation reaction for 1.5h, then cooling to 30 ℃, detecting the vitrification temperature and the weight average molecular weight of reactants after filtering, and determining that the indexes meet the requirements to obtain the fluorine-free polymer product.

Example 17

Synthesis of fluorine-free Polymer Y17:

adding 8g of emulsifier fatty alcohol polyether and 19g of deionized water into an emulsification reaction kettle, uniformly stirring, adding 20g of acrylonitrile monomer, 15g of methyl methacrylate, 9g of acrylic acid-2-ethylhexyl ester and 6g of styrene, and emulsifying for 1.0h to obtain a first emulsion;

adding 19g of deionized water and 2g of sodium dodecyl sulfate into a reaction kettle, stirring for 1h, heating to 80 ℃, adding 11% of the total weight of the first emulsion, simultaneously adding 0.2g of initiator sodium thiosulfate, heating to 90 ℃, reacting for 1h, slowly adding the remaining first emulsion and 1.8g of sodium thiosulfate when the emulsion turns blue, controlling the adding time to be 5h, heating to 95 ℃ after the addition is finished, continuing to perform heat preservation reaction for 1.5h, then cooling to 35 ℃, detecting the vitrification temperature and the weight average molecular weight of reactants after filtering, and determining that the indexes meet the requirements to obtain the fluorine-free polymer product.

Example 18

Synthesis of fluorine-free Polymer Y18:

adding 5g of emulsifier fatty alcohol polyether and 15g of deionized water into an emulsification reaction kettle, uniformly stirring, adding 20g of acrylonitrile monomer, 15g of methyl methacrylate, 9g of acrylic acid-2-ethylhexyl ester, 6g of styrene and 10g of butadiene, and emulsifying for 1.0h to obtain a first emulsion;

adding 15g of deionized water and 3g of alkylphenol ethoxylate into a reaction kettle, stirring for 1h, heating to 80 ℃, adding 10% of the total weight of the first emulsion, simultaneously adding 0.2g of initiator sodium thiosulfate, heating to 90 ℃, reacting for 1h, slowly adding the remaining first emulsion and 1.8g of sodium thiosulfate when the emulsion turns blue, controlling the adding time to be 6h, heating to 95 ℃ after the addition is finished, continuing to perform heat preservation reaction for 1.5h, then cooling to 30 ℃, detecting the vitrification temperature and the weight average molecular weight of reactants after filtering, and determining that the indexes meet the requirements to obtain the fluorine-free polymer product.

Comparative example 1

Synthesis of fluorine-free Polymer S1:

1. adding 5g of emulsifier fatty alcohol polyether and 26g of deionized water into an emulsification reaction kettle, uniformly stirring, adding 20g of methyl acrylate, 10g of butyl methacrylate and 10g of acrylic acid-2-ethylhexyl ester, and emulsifying for 1.0h to obtain a pre-emulsion;

2. adding 26g of deionized water and 1g of alkylphenol ethoxylate into a reaction kettle, stirring for 1h, heating to 80 ℃, adding 10% of the total weight of the pre-emulsion, simultaneously adding 0.2g of initiator sodium thiosulfate, heating to 90 ℃, reacting for 1h, slowly adding the remaining pre-emulsion and 1.8g of sodium thiosulfate when the emulsion turns blue, controlling the adding time to be 5h, heating to 90 ℃ after the addition is finished, continuing to perform heat preservation reaction for 1h, then cooling to 30 ℃, detecting the vitrification temperature and the weight average molecular weight of reactants after filtering, and determining that the indexes meet the requirements to obtain the fluorine-free polymer S1 sample.

Comparative example 2

Synthesis of fluorine-free Polymer S2:

1. adding 5g of emulsifier fatty alcohol polyether and 26g of deionized water into an emulsification reaction kettle, uniformly stirring, adding 10g of methyl acrylate, 10g of acrylic acid-2-ethylhexyl ester and 20g of acrylonitrile, and emulsifying for 1.0h to obtain a pre-emulsion;

2. adding 26g of deionized water and 1g of alkylphenol ethoxylate into a reaction kettle, stirring for 1h, heating to 80 ℃, adding 10% of the total weight of the pre-emulsion, simultaneously adding 0.2g of initiator sodium thiosulfate, heating to 90 ℃, reacting for 1h, slowly adding the remaining pre-emulsion and 1.8g of sodium thiosulfate when the emulsion turns blue, controlling the adding time to be 6h, heating to 90 ℃ after the addition is finished, continuing to perform heat preservation reaction for 1h, then cooling to 40 ℃, detecting the vitrification temperature and the weight average molecular weight of reactants after filtering, and determining that the indexes meet the requirements to obtain the fluorine-free polymer S2 sample.

Comparative example 3

Synthesis of fluorine-free Polymer S3:

1. adding 5g of emulsifier fatty alcohol polyether and 26g of deionized water into an emulsification reaction kettle, uniformly stirring, adding 10g of methyl acrylate, 10g of acrylic acid-2-ethylhexyl ester and 20g of styrene, and emulsifying for 1.0h to obtain a pre-emulsion;

2. adding 26g of deionized water and 1g of alkylphenol ethoxylate into a reaction kettle, stirring for 1h, heating to 80 ℃, adding 10% of the total weight of the pre-emulsion, simultaneously adding 0.2g of initiator sodium thiosulfate, heating to 90 ℃, reacting for 1h, slowly adding the remaining pre-emulsion and 1.8g of sodium thiosulfate when the emulsion turns blue, controlling the adding time to be 6h, heating to 90 ℃ after the addition is finished, continuing to perform heat preservation reaction for 1h, then cooling to 30 ℃, detecting the vitrification temperature and the weight average molecular weight of reactants after filtering, and determining that the indexes meet the requirements to obtain the fluorine-free polymer S3 sample.

Comparative example 4

Synthesis of fluorine-free Polymer S4:

adding 3g of emulsifier ethoxylated castor oil and 24g of deionized water into an emulsification reaction kettle, uniformly stirring and adding 20g of acrylonitrile monomer, 10g of acrylic acid-2-ethylhexyl ester, 8g of 1-methyl vinyl benzene and 8g of 1-butylene, and emulsifying for 1.0h to obtain a pre-emulsion;

adding 24g of deionized water and 1.5g of polypropylene glycol into a reaction kettle, stirring for 1h, heating to 60 ℃, adding 10% of the total weight of the pre-emulsion, simultaneously adding 0.15g of initiator sodium thiosulfate, heating to 60 ℃, reacting for 1h, slowly adding the remaining pre-emulsion and 1.35g of sodium thiosulfate when the emulsion turns blue, controlling the adding time to be 5h, heating to 65 ℃ after the addition is finished, continuing to perform heat preservation reaction for 1.5h, then cooling to 30 ℃, detecting the vitrification temperature and the weight average molecular weight of reactants after filtering, and determining that the indexes meet the requirements to obtain the fluorine-free polymer product.

Comparative example 5

Synthesis of fluorine-free Polymer S5:

adding 8g of emulsifier fatty alcohol polyether and 19g of deionized water into an emulsification reaction kettle, uniformly stirring, adding 20g of acrylonitrile monomer, 15g of methyl methacrylate, 9g of acrylic acid-2-ethylhexyl ester and 6g of styrene, and emulsifying for 1.0h to obtain a pre-emulsion;

adding 19g of deionized water and 2g of sodium dodecyl sulfate into a reaction kettle, stirring for 1h, heating to 90 ℃, adding 10% of the total weight of the pre-emulsion, simultaneously adding 1% of initiator sodium thiosulfate, heating to 100 ℃, reacting for 2h, slowly adding the remaining pre-emulsion and 1% of sodium thiosulfate when the emulsion turns blue, controlling the adding time to be 5h, heating to 100 ℃ after the addition is finished, continuing to perform heat preservation reaction for 2h, then cooling to 35 ℃, detecting the vitrification temperature and the weight average molecular weight of reactants after filtering, and confirming that the indexes meet the requirements to obtain the fluorine-free polymer product.

Comparative example 6

Synthesis of fluorine-free Polymer S6:

adding 5g of emulsifier fatty alcohol polyether and 15g of deionized water into an emulsification reaction kettle, uniformly stirring, adding 20g of acrylonitrile monomer, 15g of methyl methacrylate, 9g of acrylic acid-2-ethylhexyl ester, 6g of styrene and 10g of butadiene, and emulsifying for 1.0h to obtain a pre-emulsion;

adding 15g of deionized water and 3g of alkylphenol ethoxylate into a reaction kettle, stirring for 1h, heating to 80 ℃, adding 20% of the total weight of the pre-emulsion, simultaneously adding 1g of initiator sodium thiosulfate, heating to 90 ℃, reacting for 2h, slowly adding the remaining pre-emulsion and the g of sodium thiosulfate when the emulsion turns blue, controlling the adding time to be 5-6h, heating to 100 ℃ after the addition is finished, continuing to perform heat preservation reaction for 2h, then cooling to 30-40 ℃, detecting the vitrification temperature and the weight average molecular weight of reactants after filtering, and determining that the indexes meet the requirements to obtain the fluorine-free polymer product.

Test example 1

The glass transition temperature and the weight average component of the fluorine-free polymers prepared in examples 1 to 18 and comparative examples 1 to 3 were measured in the following manner, and the minimum amount of film formation and the water and oil repellency grade of the sample were measured.

(1) Glass transition temperature test:

respectively taking 30 mg of the samples of examples 1-18 and comparative examples 1-3, uniformly coating the samples on an aluminum sheet, heating and curing at 105 ℃ for 2h, then carrying out tabletting operation, placing the obtained product in a drying oven to balance to room temperature after tabletting is finished, and keeping the temperature for 0.5 h.

And (3) measuring by using a mechanical refrigeration cycle DSC, setting a temperature rise curve to be-20-100 ℃, setting a temperature rise rate to be 0.5 ℃/min, and testing the glass transition temperature of the sample.

(2) Testing the weight average molecular weight:

the samples of examples 1 to 18 and comparative examples 1 to 3 were mixed with absolute ethanol 1: 4, mixing and dissolving, centrifuging at 12000 rpm to remove supernatant, adding n-hexane with the same volume, centrifuging at 12000 rpm to remove supernatant to obtain pure fluorine-free polymer solid;

dissolving a fluorine-free polymer sample in a mobile phase, and standing overnight for use;

preparing 8 groups of weight average molecular weight standard substances in advance, dissolving in a mobile phase, and standing overnight for later use;

preparing fluidity with ultrapure water and chromatographic grade solvent by using a reverse osmosis membrane method, filtering by 0.45 mu m, and performing ultrasonic degassing for 15 min;

after GPC starting-up balance, testing 8 groups of standard substances, and drawing a molecular weight-retention time standard curve;

and testing the sample to be tested, and substituting the standard curve to obtain molecular weight data.

(3) Minimum usage test:

by minimum amount and content of non-fluorine polymer, the dry weight of the substrate needed for water and oil resistance is confirmed, thereby controlling the production and use cost of the product. Different polymers, if used in sufficient quantities, may eventually also achieve 12-grade water and oil repellency, but are too costly to be of great practical significance.

Taking a certain amount of samples of examples 1-18 and comparative examples 1-3, respectively coating on common commercially available molded paperboards, heating and curing for 30min at 105 ℃ after coating is finished, taking out, dropwise adding castor oil on a paper surface, observing whether permeation occurs or not, continuously increasing the sample amount if the permeation occurs until the castor oil cannot permeate, recording the sample amount, and performing a waterproof and oilproof test according to the sample amount.

(4) The test method for the waterproof and oil-proof performance comprises the following steps: (ii) sample treatment

The non-fluorine polymer samples of each example were taken and calculated by the actual solid content of the non-fluorine polymer samples according to dry film amounts of 1.0, 2.0, 3.0, 4.0, 5.0, 6.0, 7.0, 8.0, 9.0 and 10.0 g/m²And (5) carrying out spraying treatment on the paper pattern. After the spray coating treatment, the coating was cured at 130 ℃ for 10 min, cooled at room temperature and left to stand overnight for testing.

② oil-proof test

Referring to TAPPI-UM-557, an oil-proof grade test solution is prepared according to the table 1; after the preparation of the test solution, 0.5 mL of the test solution was dropped on the treated sample. After standing for 15 s, if the paper pattern does not leak, the oil resistance level test is passed. The highest oil resistance level (kit) that the pattern passes through is the oil resistance level of the pattern. Repeating the experiment for three times, and taking the same result twice if one of the results of the three times is inconsistent with the results of the other two times; if the two are inconsistent, the test is repeated.

TABLE 1

。

Thirdly, waterproof test:

referring to 3M-II-1988, a waterproof grade test solution was prepared according to Table 2; after the preparation of the test solution, 0.5 mL of the test solution was dropped on the treated sample. And after standing for 11 s, if the paper pattern does not leak, the waterproof grade test is passed. The highest waterproof grade number (kit) that the pattern passes through is the waterproof grade of the pattern. Repeating the experiment for three times, and taking the same result twice if one of the results of the three times is inconsistent with the results of the other two times; if the two are inconsistent, the test is repeated.

TABLE 2

。

The results of the tests (1) to (4) carried out for each of the examples and comparative examples are shown in tables 3 to 6, respectively.

TABLE 3

。

TABLE 4

。

TABLE 5

。

TABLE 6

。

As can be seen by combining tables 1 to 6, comparative examples 1 to 3 are fluorine-free polymers synthesized by using a single type or two types of monomers, and although the time and temperature parameters in the synthesis process are the same as those in examples 1 to 18, the waterproof and oil drainage performance is obviously inferior to that in examples 1 to 18; comparative examples 4 to 6 are syntheses performed by a method outside the temperature range protected by the present invention, and although the kind and content of the monomer are the same as those of examples 1 to 18, the water and oil repellency is significantly inferior to those of examples 1 to 18, because if the synthesis temperature is higher than the range of protection claimed by the present invention or the reaction time is longer than the range of protection claimed by the present invention, the polymer has a large molecular weight, a high viscosity, is not easily dispersed and spread in use, and the amount of foam is increased, so that the amount of use is increased, and holes are easily formed after the foam is eliminated in film formation, so that the water and oil repellency grade is lowered; if the synthesis temperature is lower than the range of the invention, or the reaction time is lower than the range of the invention, the molecular weight of the polymer is small, the viscosity is low, the film is not easy to form during use, the dosage is large, and the penetration from the holes of the substrate is easy, so that the film forming effect is poor, and the water and oil proofing effect is reduced.

In conclusion, only when the three monomers protected by the invention are reacted under the synthesis conditions required to be protected, the obtained fluorine-free polymer has good oil resistance and water resistance, and the raw materials and the method used in the invention are proved to have the same synergy and have obvious advantages in water resistance and oil resistance, and can meet the requirements of packaging for water resistance and oil resistance.

Example 19

Compounding the fluorine-free polymer and the sodium alginate:

adding 3g of sodium alginate and 97g of deionized water into a reaction kettle, heating to 90 ℃, and stirring for 2.0 hours to prepare a polysaccharide aqueous solution;

the polysaccharide aqueous solution and the polymer Y10 are mixed according to the ratio of 1:1 to prepare the compound polymer P1.

Example 20

Compounding a fluorine-free polymer and chitosan:

adding 1g of chitosan and 99g of deionized water into a reaction kettle, heating to 90 ℃, and stirring for 2.0 hours to obtain a polysaccharide aqueous solution;

the polysaccharide aqueous solution and the fluorine-free polymer Y5 are mixed according to the ratio of 9:1 to prepare the compound polymer P2.

Example 21

Compounding the fluorine-free polymer and the sodium alginate:

adding 10g of acetylated starch and 90g of deionized water into a reaction kettle, heating to 90 ℃, and stirring for 2.0 hours to obtain a polysaccharide aqueous solution;

the polysaccharide aqueous solution and the fluorine-free polymer Y15 are mixed according to the ratio of 4:1 to prepare the compound polymer P3.

The samples of examples 19 to 21 were tested for the minimum amount, oil repellency and water repellency by the method of test example 1, and the results are shown in Table 7.

TABLE 7

。

As can be seen from Table 7, the fluorine-free polymer can achieve good oil-proof effect when mixed with the polysaccharide high molecular material, and the dosage of the fluorine-free polymer can be reduced, because the polysaccharide high molecular material has good film-forming property and good environmental compatibility, and the film-forming property of the product can be improved after the composition is compounded with the waterproof fluorine-free polymer, so that the effects of reducing the dosage of the raw materials and ensuring the environmental protection property of the product are better are achieved.

Example 22

The fluorine-free polymer in the embodiment of the invention is compounded into an oil-proof agent, and the oil-proof agent is used for processing paper into oil-proof paper with water-proof and oil-proof functions for food packaging. The base material of the oil-proof paper is various paper, paperboard or paper-plastic products made of bamboo pulp, straw pulp, wood pulp and the like.

The formula is as follows: the fluorine-free polymer prepared in the above examples 1 to 21 was added in an amount of 20 to 70 parts by weight; the amount of the flatting agent is 0.1 to 2.5 weight parts; 0.1-1 weight part of surfactant; the dosage of the rheological regulator is 0.1 to 1 weight part; preservative with the dosage of 0.05-0.1 weight portion; 0.05 to 0.1 weight portion of pH regulator; the remaining mass was made up with distilled water.

The process comprises the following steps:

(1) preparation of oil-repellent agent

Adding 50% of water into a stirring kettle meeting the food contact material sanitation standard;

adding the planned amount of rheological control agent, and stirring for 1h under the condition of 1000-;

adding a scheduled amount of flatting agent according to the requirement of the product on glossiness in the stirring process;

stirring for 1h, and adding a planned amount of surfactant;

adding the non-fluorine polymer with the scheduled amount, and uniformly stirring;

and (4) adjusting the pH value to 5.0-7.0 by using a pH regulator, and finishing the preparation after the pH value is stable.

(2) Application method

Coating: the coating process is suitable for processing paper and paperboard, and the construction modes comprise rod coating, air knife coating, anilox roller and the like. The coating weight is 5-10 g/m of dry film²The adjustment can be carried out according to the actual situation.

Spraying: the spraying process is suitable for processing irregular products such as paper and plastics, and the suggested construction modes are air spraying, airless spraying, electrostatic spraying and the like. The spraying amount is 6-10 g/m of dry film²The adjustment can be carried out according to the actual situation.

Curing: curing at 80-130 deg.C, and heating with hot air or infrared drying equipment at 80-130 deg.C for 5 min. After full curing, standing for 24 h under the condition of cool and dry, and then preparing the oil-proof paper with the water-proof and oil-proof functions.

Example 23

Oil repellent treated paper products and gloss test

Compounding fluorine-free polymer to prepare oil-proofing agent

The compound formula is as follows:

an oil repellent agent was prepared by compounding the fluorine-free polymer of example 14, and 40g of the fluorine-free polymer of example 14, 0.05g of oleic acid polyoxyethylene ether and 0.1g of castor oil polyoxyethylene ether, 0.05g of a rheology modifier sodium polyacrylate, 0.1g of a defoaming agent polypropylene glycol, 0.03g of a pH modifier triethanolamine, and 0.1g of a preservative methylparaben were added, and the amount ranges of the matting agent fumed silica were adjusted to 0.1%, 0.2%, 0.3%, 0.4%, 0.5%, 0.6%, 0.7%, 0.8%, 0.9%, 1.0%, 1.1%, 1.2%, 1.3%, 1.4%, 1.5%, 1.6%, 1.7%, 1.8%, 1.9%, 2.0%, 2.1%, 2.2%, 2.3%, 2.4%, 2.5%, and 56.07 to 58.47g of deionized water, based on the total weight of the oil repellent agent, respectively.

The preparation method comprises the following steps:

adding 46.86g of deionized water into a stirring kettle meeting the food contact material sanitation standard, adding 0.05g of sodium polyacrylate, stirring, adjusting the rotating speed to 1200 r/min, during the stirring process, the gas phase method silicon dioxide with each content in the formula is respectively added, the stirring is carried out for 1 hour, after the gas phase method silicon dioxide is completely dispersed, adding 0.05g of oleic acid polyoxyethylene ether, adjusting the rotation speed to 600 r/min, stirring for 5min, continuously adding 0.1g of castor oil polyoxyethylene ether, keeping the rotation speed to 600 r/min, stirring for 5min, adding 40g of the fluorine-free polymer in the example 14 and 9.21-11.61 g of water, stirring for 1h, adding 0.1g of polypropylene glycol-1200 and 0.1g of methyl paraben, stirring for 10 min, finally adding 0.03g of triethanolamine, adjusting the pH value to 7.5-8.5, and spraying the sample after the stability is confirmed to be qualified by stirring for 10 min.

Sample treatment

Adopting the oil-proofing agent prepared in the step (i), wherein the dry film amount is 10.0 g/m²Carrying out spraying treatment on the paper pattern; after the spray coating treatment, the coating was cured at 130 ℃ for 10 min, cooled at room temperature and left to stand overnight for testing.

③ measurement of glossiness

After the sample is prepared, the incident light irradiates the surface of the sample at 45 degrees and 90 degrees respectively, and the reflection condition is observed. The mirror reflection means that the whole paper pattern has obvious reflection phenomenon and good glossiness; the partial reflection means that the paper pattern partially reflects light or appears a bright band with a texture shape and spots, and the glossiness is general; "dull" means that the paper pattern is non-reflective and non-glossy.

The gloss of the surface of the sample was measured using a paper gloss tester. Adjusting the incident angle of incident light to 75 +/-0.1 degrees, and measuring a paper pattern after correcting the instrument by using a standard plate by using a reference method of TAPPI T480 om-09. The relationship between the amount of fumed silica and the gloss is shown in Table 8:

TABLE 8

。

As can be seen from Table 8, the fluorine-free polymer of the embodiment of the present invention can adjust the 75 ° incident light reflectance of the paper substrate to be adjustable within a range of 8.74% to 87.33% by adjusting the addition amount of the matting agent.

Example 24

Fluorine-free polymer as oil-proof component of food packaging material and anti-adhesion test:

compounding fluorine-free polymer to prepare oil-proof component

The compound formula is as follows:

the fluorine-free polymers of examples 2 to 3 and comparative example 1 were each compounded as an oil-repellent component, and 20g of the fluorine-free polymers of examples 2 to 3 and comparative example 1 were each added with 0.5g of octyl/decyl glucoside as a surfactant, 1g of hydroxyethyl methyl cellulose-4000 as a rheology modifier, 0.1g of polypropylene glycol-1200 as an antifoaming agent, 0.05g of acetic acid as a pH modifier, 0.1g of methyl paraben as a preservative, 77.25g of deionized water, and 1g of fumed silica.

The preparation method comprises the following steps:

adding 61.8g of water into a stirring kettle meeting the food contact material sanitation standard, adding 1g of hydroxyethyl methylcellulose-4000, starting stirring, adjusting the rotating speed to 1200 r/min, adding 1g of fumed silica during stirring, stirring for 1h, adding 0.5g of octyl/decyl glucoside after the fumed silica is completely dispersed, adjusting the rotating speed to 600 r/min, stirring for 10 min, adding 20g of the fluorine-free polymer of example 2 and 15.55g of water, stirring for 1h, adding 0.1g of polypropylene glycol-1200 and 0.1g of methylparaben, stirring for 10 min, finally adding 0.05g of acetic acid, adjusting the pH value to 5.0-7.0, and stirring for 10 min.

The oil-repellent component of example 3 and comparative example 1 were prepared in the same manner as the oil-repellent component of example 2.

Adhesion prevention test:

selecting paper discs with the same shape and weight and different types of oil-proof components according to the dry film amount of 10.0 g/m²Respectively carrying out spraying treatment on the inner surfaces of the bottoms of the left side and the right side of the paper disc; after the coating treatment is finished, performing heat curing at 130 ℃ for 10 min, cooling at room temperature, standing overnight, and then testing; putting a whole dish of rice in the treated paper tray, and treating in an oven at 150 deg.C for 30 min; the removable rice was gently scraped off with a spoon to confirm the effect of adhesion resistance of the sample. The results are shown in FIGS. 2-3, where 12 is the sample treated in comparative example 1 on the left and example 2 on the right; in FIG. 2, the blank sample without any treatment is shown on the left side, and the sample treated in example 3 is shown on the right side.

As can be seen from FIGS. 1-2, after the fluorine-free polymers of examples 2 and 3 of the present invention were prepared as oil-repellent components and sprayed on the plates of foods, the corresponding food packaging cases had little adhesion to cooked rice.

Test example 2

The leaching test of the fluorine-free polymer of the embodiment 1-21 of the invention is carried out by the following test method:

using the usual commercially available molded paperboard, the fluorine-free polymers of examples 1 to 21 above were used in an amount of 10 g/m²Coating with the application amount, curing at 80 ℃ for 5min to obtain a treatment group sample, setting an uncured blank control group, and soaking the sample strips in the corresponding test solutions in the table 8 respectively.

The harmful elements migrate, and the results are shown in table 9:

TABLE 9

。

Note: ICP has no organic phase mercury standard product, so that the content of 95% ethanol water solution and isooctane mercury element is not determined.

As can be seen from Table 9, the fluorine-free polymers of examples 1-21 were treated to remove trace amounts of the four common harmful elements of Pb, Cd, Hg and As after application to molded paperboard.

Component migration:

the sample of example 5 was analyzed by LC-MS using the treatment method shown in Table 6 together with a blank control, and LC-MS spectra of the sample under each treatment method are shown in FIG. 1, and deionized water and blank control are shown from top to bottom in FIG. 3; deionized water at 60 ℃ for 2 h; 4% aqueous acetic acid, blank control; 4% acetic acid water solution, 60 ℃, 2 h; 95% ethanol aqueous solution, blank control; 95% ethanol water solution, 60 ℃, 2 h; isooctane, blank control; isooctane, 45 ℃, 0.5h of LC-MS spectrogram after treatment. As can be seen in fig. 3, no significant migration was found after the non-fluoropolymer of example 5 was applied to the molded paperboard.

Finally, it should be noted that: the above embodiments are only used to illustrate the technical solution of the present invention, and not to limit the same; while the invention has been described in detail and with reference to the foregoing embodiments, it will be understood by those skilled in the art that: the technical solutions described in the foregoing embodiments may still be modified, or some or all of the technical features may be equivalently replaced; and the modifications or the substitutions do not make the essence of the corresponding technical solutions depart from the scope of the technical solutions of the embodiments of the present invention.

Claims

1. A fluorine-free polymer, wherein said fluorine-free polymer is copolymerized from monomers consisting essentially of:

component (A) acrylonitrile monomer;

CH₂(= O) -O-Y of formula 1

component (C) is a vinyl aromatic monomer and/or an olefinic monomer.

2. The fluorine-free polymer according to claim 1, wherein the component (B) is any one or more selected from the group consisting of methyl acrylate, ethyl acrylate, butyl acrylate, methyl methacrylate, ethyl methacrylate, butyl methacrylate, cyclohexyl acrylate, 2-ethylhexyl acrylate, cyclohexyl methacrylate, and 2-ethylhexyl methacrylate.

3. The fluorine-free polymer according to claim 1, wherein the vinyl aromatic monomer in the component (C) is any one selected from the group consisting of styrene, 1-methylvinylbenzene, divinylbenzene; the olefin monomer is selected from any one of ethylene, vinyl acetate, propylene, 1-butylene and butadiene.

4. The fluorine-free polymer according to any one of claims 1 to 3, wherein the fluorine-free polymer has a glass transition temperature of-30 to 40 ℃.

5. The fluorine-free polymer according to any one of claims 1 to 3, wherein the weight average molecular weight of the fluorine-free polymer is 20 to 70 ten thousand.

6. The fluorine-free polymer according to any one of claims 1 to 3, wherein the component (A) is 30 to 60wt% based on the total weight of the fluorine-free polymer monomer.

7. The fluorine-free polymer according to any one of claims 1 to 3, wherein the weight ratio of the component (A), the component (B) and the component (C) is 1:0.5 to 1.2:0.3 to 0.8.

8. The fluorine-free polymer according to any one of claims 1 to 7, wherein the fluorine-free polymer further comprises a polysaccharide type high molecular material.

9. The fluorine-free polymer according to claim 8, wherein the polysaccharide polymer material includes but is not limited to sodium alginate, chitosan, acetylated starch.

10. A process for the preparation of the fluorine-free polymer according to any one of claims 1 to 9, wherein the reaction of component (a), component (B), component (C) is carried out in the presence of an emulsifier, an initiator and water, and in particular:

11. The method of claim 10, wherein the emulsifier comprises an anionic emulsifier and/or a nonionic emulsifier;

wherein the anionic emulsifier is any one or more of sodium dodecyl sulfate, sodium dodecyl alcohol polyoxyethylene ether sulfate or ammonium alkyl phenol ethoxylate sulfate;

the non-ionic emulsifier is selected from one or more of polyoxyethylene sorbitan fatty acid ester, sugar ester, polyether surfactant, acetylene glycol surfactant, polyethylene glycol, polypropylene glycol, ethoxylated castor oil, oleic acid ethoxylate, alkylphenol ethoxylate, and copolymer of organosilicon and polyether.

12. The method of claim 10, wherein the initiator is any one or more of ammonium persulfate, potassium persulfate, and sodium thiosulfate.

13. The method of claim 10, further comprising:

14. The method according to claim 13, characterized in that the first emulsification is carried out in particular by:

15. The method of claim 13, wherein the second emulsifying the first emulsion and polymerizing comprises a first polymerization and a second polymerization, and specifically comprises:

16. An oil-repellent agent, characterized in that it comprises a fluorine-free polymer and an auxiliary agent; wherein the fluorine-free polymer is mainly copolymerized by the following monomers:

component (A) acrylonitrile monomer;

CH₂(= O) -O-Y of formula 1

component (C) is a vinyl aromatic monomer and/or an olefinic monomer.

17. The oil-repellent agent according to claim 16, wherein the component (B) is one or more selected from the group consisting of methyl acrylate, ethyl acrylate, butyl acrylate, methyl methacrylate, ethyl methacrylate, butyl methacrylate, cyclohexyl acrylate, 2-ethylhexyl acrylate, cyclohexyl methacrylate and 2-ethylhexyl methacrylate.

18. The oil-repellent agent according to claim 16, wherein the vinyl aromatic monomer in the component (C) is any one selected from styrene, 1-methylvinylbenzene, divinylbenzene; the olefin monomer is selected from any one of ethylene, vinyl acetate, propylene, 1-butylene and butadiene.

19. The oil-repellent agent according to any one of claims 16 to 18, wherein the glass transition temperature of the fluorine-free polymer is-30 to 40 ℃.

20. The oil-repellent agent according to any one of claims 16 to 18, wherein the weight average molecular weight of the fluorine-free polymer is 20 to 70 ten thousand.

21. The oil-repellent agent according to any one of claims 16 to 18, wherein the component (a) accounts for 30 to 60wt% of the total weight of the fluorine-free polymer monomer.

22. The oil-repellent agent according to any one of claims 16 to 18, wherein the weight ratio of the component (a), the component (B) and the component (C) is 1:0.5 to 1.2:0.3 to 0.8.

23. An oil-repellent agent according to any of claims 16 to 22, wherein the adjuvant comprises, but is not limited to, any one or more of surfactants, rheology modifiers, defoamers, preservatives, matting agents and pH modifiers.

24. The oil-repellent agent according to any one of claims 14 to 23, wherein the fluorine-free polymer further comprises a polysaccharide polymer material.

25. The oil-repellent agent according to claim 24, wherein the polysaccharide polymer material includes, but is not limited to, sodium alginate, chitosan, and acetylated starch.

26. A paper product treated with an oil-repellent agent as claimed in any one of claims 16 to 25.

27. Use of a fluorine-free polymer in an oil-repellent component of a paper packaging material for food, characterized in that the fluorine-free polymer is mainly copolymerized from the following monomers:

component (A) acrylonitrile monomer;

CH₂(= O) -O-Y of formula 1

component (C) is a vinyl aromatic monomer and/or an olefinic monomer.

28. The use according to claim 27, wherein component (B) is selected from any one or more of methyl acrylate, ethyl acrylate, butyl acrylate, methyl methacrylate, ethyl methacrylate, butyl methacrylate, cyclohexyl acrylate, 2-ethylhexyl acrylate, cyclohexyl methacrylate, 2-ethylhexyl methacrylate.

29. The use according to claim 27, wherein the vinyl aromatic monomer in component (C) is selected from any one of styrene, 1-methyl vinyl benzene, divinylbenzene, and the olefinic monomer is selected from any one of ethylene, vinyl acetate, propylene, 1-butene, butadiene.

30. The use according to any one of claims 27 to 29, wherein the non-fluoropolymer has a glass transition temperature of-30 to 40 ℃.

31. The use according to any one of claims 27 to 29, wherein the non-fluoropolymer has a weight average molecular weight of 20 to 70 ten thousand.

32. Use according to any one of claims 27 to 29, wherein component (a) represents 30 to 60wt% of the total weight of the non-fluoropolymer monomer.

33. The use according to any one of claims 27 to 29, wherein the weight ratio of component (a), component (B) and component (C) is 1:0.5 to 1.2:0.3 to 0.8.

34. The use according to any one of claims 27 to 33, wherein the fluorine-free polymer further comprises a polysaccharide-based polymer material.

35. The use of claim 34, wherein the polysaccharide polymer material comprises but is not limited to sodium alginate, chitosan, acetylated starch.