A non-fluorinated polymer and treating agent

Abstract

The present invention provides a non-fluorine polymer and a treatment agent containing the polymer, including the following components in mass percentage: 5 to 35 wt% of a non-fluorine polymer component; 0 to 8 wt% of a surfactant; 0 to 15 wt% of a component; and the balance is deionized water. The non-fluorine polymer component includes a non-fluorine polymer produced by polymerization in the presence of a chain transfer agent and a polymerization initiator: a silicon-containing acrylate monomer (a) and a non-silicon comonomer (b), wherein the non-silicon comonomer (b) is at least one of (b1) and (b2), (b1) an acrylate monomer having a saturated hydrocarbon group or a cyclic hydrocarbon group with a carbon number of 1 to 30; and (b2) is a functional monomer. The non-fluorine polymer prepared based on the silicon-containing acrylate monomer of the present invention or the treatment agent containing the polymer imparts excellent hydrophobicity and oleophobicity to substrates such as fibers.

Description

Technical Field

[0001] The invention relates to the technical field of dyeing and finishing auxiliaries, in particular to a non-fluorine polymer and a treating agent containing the polymer. Background Art

[0002] Inspired by bionics, waterproof processing materials are widely used in various industries, such as clothing fabrics, food packaging, construction, home furnishing, electronics, aerospace, etc., which can give products excellent waterproof functions. Organic fluorine waterproofing agents (especially octafluoro waterproofing agents) occupy a major market share due to their high water repellency, but they have disadvantages such as high toxicity and difficulty in degradation. As early as 2012, the Stockholm Convention on Persistent Organic Pollutants listed PFOA (perfluorooctanoic acid) and PFOS (perfluorooctane sulfonic acid) in the list of chemicals to be banned. Today, as the concept of ecological environmental protection is becoming increasingly popular, fluorine-free waterproofing agents are more easily accepted by consumers, so the development of fluorine-free waterproofing agents has become a new research hotspot.

[0003] Ordinary fluorine-free waterproofing agents containing long-chain alkyl groups have a certain loss of waterproof performance due to the lack or incomplete crystal surface structure. When the critical surface tension is close to that of liquids such as water and milk, these liquids will wet the fabric; and during the contact process with water or oil, when the water temperature or oil temperature is higher than the melting temperature of the long-chain alkyl crystal, it will not be able to maintain its hydrophobic and oleophobic properties. Therefore, in order to solve this problem, by introducing silicon-containing polyacrylate segments, the surface tension of non-fluorinated polymers is reduced, and the hydrophobic and oleophobic properties of the treatment agent are improved, especially the high-temperature oil resistance. Summary of the invention

[0004] The purpose of the present invention is to provide a non-fluorine polymer and a treatment agent containing the polymer, which can impart excellent hydrophobicity and oleophobicity to substrates such as fibers, and is green, environmentally friendly, and harmless to human health, thereby overcoming the shortcomings of the prior art.

[0005] In order to solve the above technical problems, the present invention is achieved through the following technical solutions: a non-fluorinated polymer and a treating agent containing the polymer, wherein the components and mass percentages are as follows:

[0006] The non-fluorine polymer component is 5-35wt%; the surfactant is 0-8wt%; the auxiliary agent is 0-15wt%; and the balance is deionized water.

[0007] The non-fluorine polymer component comprises: a silicon-containing acrylate monomer (a) and a non-silicon comonomer (b), wherein the non-silicon comonomer (b) is at least one of (b1) and (b2), (b1) an acrylate monomer having a saturated hydrocarbon group or a cyclic hydrocarbon group with a carbon number of 1 to 30; and (b2) a functional monomer, wherein the monomers (a) and (b) are polymerized in the presence of a chain transfer agent and a polymerization initiator to produce the non-fluorine polymer.

[0008] The silicon-containing acrylate monomer (a) is a silicon-containing acrylate or a derivative thereof, and its general structural formula is:

[0009]

[0010] Where X 1 , X 2 and X 3 H, CH 3 , Cl or Br; Y is a chemical single bond or -NH-, -NR 2 -、-NH-CO-、-NR 2 -CO-, -NHCONH-, -NHCOO-, -NH-SO 2 -、-NR 2 -SO 2 -one or more; n is any integer of 1, 2, 3, 4.

[0011] Z 1 , Z 2 and Z 3 The structural formula is:

[0012]

[0013] In the formula, A is a chemical single bond or an oxygen atom, R 1 , R 2 and R 3 is a saturated hydrocarbon group or a cyclic hydrocarbon group having 1 to 30 carbon atoms; and m is an integer of 0 to 300.

[0014] The silicon-containing acrylate monomer (a) may be one substance or a mixture of multiple substances conforming to the general formula.

[0015] The non-silicon comonomer (b) is at least one of an acrylate monomer (b1) and a functional monomer (b2) having a saturated hydrocarbon group or a cyclic hydrocarbon group with 1 to 30 carbon atoms.

[0016] The structural formula of the acrylic acid ester monomer (b1) having a saturated hydrocarbon group or a cyclic hydrocarbon group having 1 to 30 carbon atoms is:

[0017] CH 2 =C(R 4 )COOR 5

[0018] In the formula, R 4 H or CH 3 , R 5 It is a saturated hydrocarbon group or a cyclic hydrocarbon group having 1 to 30 carbon atoms.

[0019] The functional monomer (b2) is selected from one or more of glycidyl (meth)acrylate, acrylamide, diacetone acrylamide combined with adipic dihydrazide system, ethylene glycol dimethacrylate, trimethylolpropane tri(meth)acrylate, divinylbenzene, dimethylaminoethyl (meth)acrylate, (methoxy)polyethylene glycol (meth)acrylate, (meth)acryloyloxyethyltrimethylammonium chloride, N-acryloyl pyrrolidone, 3-chloro-2-hydroxy-propyl methacrylate, hydroxyethyl (meth)acrylate, hydroxymethyl (meth)acrylate, vinyl chloride, vinylidene chloride, butadiene, isoprene, and chloroprene.

[0020] The chain transfer agent is alkyl mercaptan.

[0021] The polymerization initiator is an azo-based, peroxide-based, or redox-based polymerization initiator.

[0022] The surfactant includes one or more of a cationic surfactant, an anionic surfactant and a nonionic surfactant.

[0023] The nonionic surfactant is one or more of ether, ester, ester ether, alkanolamide, polyol and amine oxide;

[0024] The cationic surfactant is one or more of amine, amine salt, quaternary ammonium salt, imidazoline and imidazolinium salt.

[0025] The anionic surfactant is one or more of carboxylic acid derivatives, sulfonates, sulfate esters, phosphate esters, and N-acylaminocarboxylates.

[0026] The auxiliary agents include pH adjusting auxiliary agents and auxiliary solvents.

[0027] The pH adjusting auxiliary agent includes acid, alkali or amino acid, and makes the pH value of the waterproof and oil-proof agent between 2 and 7.

[0028] The auxiliary solvent is selected from dipropylene glycol, tripropylene glycol, dipropylene glycol ethyl ether, tripropylene glycol ethyl ether, acetone, methyl ethyl ketone, ethyl acetate, n-propyl acetate, butyl acetate, N-methyl-2-pyrrolidone, N, N-dimethylformamide, isopropyl alcohol, n-propyl alcohol, or a mixture of two thereof.

[0029] The present invention has the following beneficial effects:

[0030] The present invention is based on reducing the surface tension of non-fluorine polymers by introducing silicon-containing polyacrylate segments, thereby imparting durable and stable low surface energy to substrates such as fibers, especially high-temperature oil resistance and high-temperature water resistance, and the effect is comparable to that of fluorine-based waterproofing agents; and the polymer of the present invention avoids the use of fluorine-containing acrylate monomers, is environmentally friendly, and has high commercial value. DETAILED DESCRIPTION

[0031] The technical solutions in the embodiments of the present invention are described clearly and completely below. Obviously, the described embodiments are only part of the embodiments of the present invention, not all of the embodiments. Based on the embodiments of the present invention, all other embodiments obtained by ordinary technicians in this field without creative work are within the scope of protection of the present invention.

[0032] In order to verify the high-temperature oil resistance and high-temperature water resistance of the non-fluorinated polymer and the treating agent containing the polymer of the present invention, the test methods used hereinafter are as follows.

[0033] [Preparation of pulp molded products]

[0034] A mixture of 70 parts of bagasse pulp and 30 parts of bamboo pulp is beaten into a pulp slurry with a water filtration degree of 550 ml (Canadian freeness) and a pulp concentration of 0.5wt%. Then, 0.1-0.2%wt% retention aid and 5wt% and 8wt% of the synthesized treatment agent, which are respectively 5wt% and 8wt% of the dry paper weight, are added and stirred evenly.

[0035] The above-mentioned pulp slurry is added to a metal tank. A metal pulp mold forming die having a plurality of suction holes is present at the lower part of the tank with a mesh body arranged thereon. A vacuum pump is used to suck and dehydrate the pulp-containing aqueous composition from the side of the pulp mold forming die opposite to the side where the mesh body is arranged through the pulp mold forming die and the mesh body, and the solid components (pulp, etc.) contained in the pulp-containing aqueous composition are accumulated on the mesh body to obtain a pulp mold intermediate. Next, the obtained pulp mold intermediate is pressurized from top to bottom using a metal molding positive mold and a molding negative mold heated to 60-200°C to dry it. In this way, a pulp molded product molded into a container shape is manufactured.

[0036] [High temperature oil resistance]

[0037] 100 ml of an evaluation liquid (corn oil) at 100°C was injected into a pulp molded product formed into a container, and after standing for 30 minutes, the evaluation liquid was discarded and the degree of bleeding of the evaluation liquid to the pulp molded product (container) was visually evaluated according to the following criteria.

[0038] 4: There is almost no oil stain on the inside of the bottom of the pulp molded container.

[0039] 3: No oil stains were found on the outside of the bottom of the pulp molded container.

[0040] 2: Less than 5% of the visible oil stains are visible on the outside of the bottom of the pulp molded container.

[0041] 1: The outer side of the bottom of the pulp molded container has visible oil stains covering more than 5% and less than 50% of the area.

[0042] 0: Oil stains covering more than 50% of the outer surface of the bottom of the pulp molded container are visible.

[0043] [High temperature water resistance]

[0044] 100 ml of an evaluation liquid (tap water) at 100° C. was injected into a pulp molded product formed into a container, and after standing for 30 minutes, the evaluation liquid was discarded, and the degree of bleeding of the evaluation liquid to the pulp molded product (container) was visually evaluated according to the following criteria.

[0045] 4: There is almost no water stain on the inside of the bottom of the pulp molded container.

[0046] 3: No water stains were found on the outside of the bottom of the pulp molded container.

[0047] 2: Less than 5% of the visible water stains are on the outside of the bottom of the pulp molded container.

[0048] 1: Water stains covering more than 5% and less than 50% of the visible area on the outside of the bottom of the pulp molded container.

[0049] 0: Water stains covering more than 50% of the outer surface of the bottom of the pulp molded container are visible.

[0050] Example 1

[0051] 20.0 g of ethyl acetate, 12.0 g of 3-methacryloxypropyltriisopropoxysilane, 3.0 g of dimethylaminoethyl methacrylate (DM) and 0.5 g of n-dodecyl mercaptan were added to a 250 mL four-necked flask equipped with a stirring device, a thermometer, a reflux condenser, a nitrogen inlet and a heating device, and the mixture was evacuated and replaced with nitrogen three times. The temperature was slowly raised to 75-78° C., 0.3 g of initiator azobisisobutyronitrile (AIBN) was added, and the mixture was mixed and stirred under a nitrogen atmosphere for 18 h to obtain a polymer solution.

[0052] 0.5 g of acetic acid and 83.5 g of deionized water were added to the obtained polymer solution and stirred for 0.5 h to disperse evenly. Then, ethyl acetate was distilled off under reduced pressure while heating to obtain a non-fluorinated polymer emulsion with a solid content of 15 wt% (the content of volatile organic solvents is less than 1 wt%).

[0053] Example 2

[0054] Exactly the same as Example 1, except that 3-chloroacryloxypropyltriisopropoxysilane was used instead of 3-methacryloxypropyltriisopropoxysilane.

[0055] Example 3

[0056] 20.0 g of isopropanol, 12.0 g of 3-chloroacryloxypropyltris(trimethylsiloxy)silane, 1.0 g of octadecyl acrylate, 2.0 g of hydroxymethyl methacrylate and 0.5 g of n-octadecyl mercaptan were added to a 250 mL four-necked flask equipped with a stirring device, a thermometer, a reflux condenser, a nitrogen inlet and a heating device, and the mixture was evacuated and replaced with nitrogen three times. The temperature was slowly raised to 75-78° C., 0.3 g of initiator azobisisobutyronitrile (AIBN) was added, and the mixture was mixed and stirred under a nitrogen atmosphere for 18 h to obtain a polymer solution.

[0057] 0.5 g of acetic acid and 83.5 g of deionized water were added to the obtained polymer solution and stirred for 0.5 h to disperse evenly. Then, isopropanol was distilled off under reduced pressure while heating to obtain a non-fluorinated polymer emulsion with a solid content of 15 wt% (the content of volatile organic solvents was less than 1 wt%).

[0058] Embodiment 4-6

[0059] Exactly the same as Example 3, except that 2,3-dichloroacryloxypropyl tris(trimethylsiloxy)silane (Example 4), 2,3-dichloroacryloxypropyl triisopropoxysilane (Example 5), 3-methacryloxypropyl tris(trimethylsiloxy)silane (Example 6) were used instead of 3-chloroacryloxypropyl tris(trimethylsiloxy)silane.

[0060] Example 7

[0061] 20.0 g of methyl ethyl ketone, 10.0 g of 3-chloroacryloxypropyltrimethoxysilane, 3.6 g of dodecyl methacrylate, 0.8 g of glycidyl (meth)acrylate, 0.6 g of hydroxyethyl methacrylate and 0.5 g of n-octadecyl mercaptan were added to a 250 mL four-necked flask equipped with a stirring device, a thermometer, a reflux condenser, a nitrogen inlet and a heating device, and the mixture was evacuated and replaced with nitrogen three times. The temperature was slowly raised to 75-78° C., 0.3 g of initiator azobisisobutyronitrile (AIBN) was added, and the mixture was mixed and stirred under a nitrogen atmosphere for 18 h to obtain a polymer solution.

[0062] 0.2 g of octadecyltrimethylammonium chloride, 1.0 g of lauryl alcohol polyoxyethylene ether (AEO-20), 0.5 g of acetic acid and 82.8 g of deionized water were added to the obtained polymer solution and stirred for 0.5 h to disperse evenly. Then, methyl ethyl ketone was distilled off under reduced pressure while heating to obtain a non-fluorinated polymer emulsion with a solid component solubility of 16 wt% (the content of volatile organic solvents is less than 1 wt%).

[0063] Embodiment 8-9

[0064] Exactly the same as Example 7, except that 2,3-dichloroacryloxypropyltrimethoxysilane (Example 8) or acryloxypropyltrimethoxysilane (Example 9) was used instead of 3-chloroacryloxypropyltrimethoxysilane.

[0065] Comparative Example 1

[0066] 20.0 g of isopropanol, 12.0 g of octadecyl acrylate, 3.0 g of dimethylaminoethyl methacrylate (DM) and 0.5 g of n-dodecyl mercaptan were added to a 250 mL four-necked flask equipped with a stirring device, a thermometer, a reflux condenser, a nitrogen inlet and a heating device, and the mixture was evacuated and replaced with nitrogen three times. The temperature was slowly raised to 75-78° C., 0.3 g of initiator azobisisobutyronitrile (AIBN) was added, and the mixture was mixed and stirred under a nitrogen atmosphere for 18 h to obtain a polymer solution.

[0067] 0.5 g of acetic acid and 83.5 g of deionized water were added to the obtained polymer solution and stirred for 0.5 h to disperse evenly. Then, isopropanol was distilled off under reduced pressure while heating to obtain a non-fluorinated polymer emulsion with a solid content of 15 wt% (the content of volatile organic solvents was less than 1 wt%).

[0068] Comparative Example 2

[0069] 20.0 g of methyl ethyl ketone, 12.0 g of dodecyl acrylate, 3.0 g of dimethylaminoethyl methacrylate (DM) and 0.5 g of n-dodecyl mercaptan were added to a 250 mL four-necked flask equipped with a stirring device, a thermometer, a reflux condenser, a nitrogen inlet and a heating device, and the mixture was evacuated and replaced with nitrogen three times. The temperature was slowly raised to 75-78° C., 0.3 g of initiator azobisisobutyronitrile (AIBN) was added, and the mixture was mixed and stirred under a nitrogen atmosphere for 18 h to obtain a polymer solution.

[0070] 0.5 g of acetic acid and 83.5 g of deionized water were added to the obtained polymer solution and stirred for 0.5 h to disperse evenly. Then, methyl ethyl ketone was distilled off under reduced pressure while heating to obtain a non-fluorinated polymer emulsion with a solid component solubility of 15 wt% (the content of volatile organic solvents is less than 1 wt%).

[0071] Comparative Example 3

[0072] 20.0 g of methyl ethyl ketone, 12.0 g of octadecyl methacrylate, 3.0 g of dimethylaminoethyl methacrylate (DM) and 0.5 g of n-dodecyl mercaptan were added to a 250 mL four-necked flask equipped with a stirring device, a thermometer, a reflux condenser, a nitrogen inlet and a heating device, and the mixture was evacuated and replaced with nitrogen three times. The temperature was slowly raised to 75-78° C., 0.3 g of initiator azobisisobutyronitrile (AIBN) was added, and the mixture was mixed and stirred under a nitrogen atmosphere for 18 h to obtain a polymer solution.

[0073] 0.2 g of octadecyltrimethylammonium chloride, 0.8 g of isomeric tridecyl alcohol polyoxyethylene ether (13 / 80), 0.5 g of acetic acid and 82.5 g of deionized water were added to the obtained polymer solution and stirred for 0.5 h to disperse evenly. Then, methyl ethyl ketone was distilled off under reduced pressure while heating to obtain a non-fluorinated polymer emulsion with a solid component solubility of 16 wt% (the content of volatile organic solvents is less than 1 wt%).

[0074] Performance Testing

[0075] Table 1 shows the evaluation results of high temperature oil resistance and high temperature water resistance of pulp molded articles obtained by using the non-fluorine polymer emulsions of Examples 1 to 9 and Comparative Examples 1 to 3 as treating agents.

[0076] Table 1

[0077]

[0078] The preferred embodiments of the present invention disclosed above are only used to help illustrate the present invention. The preferred embodiments do not describe all the details in detail, nor do they limit the invention to the specific implementation methods described. Obviously, many modifications and changes can be made according to the content of this specification. This specification selects and specifically describes these embodiments in order to better explain the principles and practical applications of the present invention, so that those skilled in the art can understand and use the present invention well. The present invention is limited only by the claims and their full scope and equivalents.

Claims

1. A non-fluorinated polymer, characterized in that A silicon-containing acrylate monomer (a) and a non-silicon comonomer (b), wherein the non-silicon comonomer (b) is at least one of (b1) and (b2), (b1) is an acrylate monomer having a saturated hydrocarbon group or a cyclic hydrocarbon group having 1 to 30 carbon atoms; (b2) is a functional monomer, wherein the silicon-containing acrylate monomer (a) and the non-silicon comonomer (b) are polymerized in the presence of a chain transfer agent and a polymerization initiator to produce the non-fluorinated polymer; The silicon-containing acrylate monomer (a) is 3-chloroacryloxypropyl triisopropoxysilane, 3-chloroacryloxypropyl tris(trimethylsiloxy)silane, or 3-dichloroacryloxypropyl tris(trimethylsiloxy)silane.

2. The non-fluorinated polymer according to claim 1, characterized in that The non-silicon comonomer (b) is at least one of an acrylate monomer (b1) having a saturated hydrocarbon group or a cyclic hydrocarbon group with 1 to 30 carbon atoms and a functional monomer (b2), and the structural formula of (b1) is: CH2=C(R4)COOR5 In the formula, R4 is H or CH3, and R5 is a saturated hydrocarbon group or a cyclic hydrocarbon group having 1 to 30 carbon atoms.

3. The non-fluorinated polymer according to claim 1, characterized in that (b2) is selected from one or more of glycidyl (meth)acrylate, acrylamide, diacetone acrylamide combined with adipic dihydrazide system, ethylene glycol dimethacrylate, trimethylolpropane tri(meth)acrylate, divinylbenzene, dimethylaminoethyl (meth)acrylate, (methoxy)polyethylene glycol (meth)acrylate, (meth)acryloyloxyethyltrimethylammonium chloride, N-acryloyl pyrrolidone, 3-chloro-2-hydroxy-propyl methacrylate, hydroxyethyl (meth)acrylate, hydroxymethyl (meth)acrylate, vinyl chloride, vinylidene chloride, butadiene, isoprene, and chloroprene.

4. The non-fluorinated polymer according to claim 1, characterized in that The chain transfer agent is alkyl mercaptan, and the polymerization initiator is an azo-based, peroxide-based, or redox-based polymerization initiator.

5. A treatment agent, characterized in that The components and their mass percentages are as follows: 5-35 wt% non-fluorine polymer, 0-8 wt% surfactant, 0-15 wt% additive, and the balance is deionized water; the non-fluorine polymer is a non-fluorine polymer according to any one of claims 1 to 4.

6. The treatment agent according to claim 5, characterized in that The nonionic surfactant is one or more of ethers, esters, ester ethers, alkanolamides, polyols and amine oxides.

7. The treatment agent according to claim 5, characterized in that The cationic surfactant is one or more of an amine, an amine salt, an imidazoline, and an imidazolinium salt.

8. The treatment agent according to claim 5, characterized in that The anionic surfactant is one or more of carboxylic acid derivatives, sulfonates, sulfate esters, phosphate esters, and N-acylaminocarboxylates.

9. The treatment agent according to claim 5, characterized in that The auxiliary agent includes a pH adjusting auxiliary agent and an organic solvent; the pH adjusting auxiliary agent includes an acid, a base or an amino acid, and makes the pH value of the treating agent between 2 and 9.

10. The treatment agent according to claim 9, characterized in that The organic solvent is selected from one or a mixture of two of dipropylene glycol, tripropylene glycol, dipropylene glycol ethyl ether, tripropylene glycol ethyl ether, acetone, methyl ethyl ketone, ethyl acetate, n-propyl acetate, butyl acetate, N-methyl-2-pyrrolidone, N,N-dimethylformamide, isopropanol, and n-propanol.

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