阅读说明：本技术 一种无氟阳离子聚丙烯酸酯防水剂及其制备方法 (A kind of free-floride cationic polyacrylate waterproofing agent and preparation method thereof ) 是由 钟少锋 吉婉丽 祝良荣 刘晓云 张奇鹏 于 2019-08-22 设计创作，主要内容包括：本发明提供一种织物品专用高效无氟防水剂及其制备工艺和应用,所述无氟防水剂按质量百分比包括以下组分：无氟聚合物20-30％、表面活性剂1-4％、助剂0.5-2.5％和水。本发明提供的无氟防水剂具有良好的防水效果,不含氟元素,并且绿色环保。(The present invention provides a kind of fabric product special efficient without fluoro water proofing agent and its preparation process and application, and the no fluoro water proofing agent includes following components by mass percentage: fluorine free polymer 20-30%, surfactant 1-4%, auxiliary agent 0.5-2.5% and water.No fluoro water proofing agent provided by the invention has good waterproof effect, is free of fluorine element, and environmentally protective.)

1. a kind of free-floride cationic polyacrylate waterproofing agent, which is characterized in that each component and mass percent are as follows:

Fluorine free polymer 20%-30%, surfactant 1-4%, auxiliary agent 0.25-2.5%, surplus are water；

The fluorine free polymer passes through the free radical polymerization by initiator thermal decomposition generation by hydrophobic monomer and function monomer I-III It forms, the hydrophobic monomer and function monomer account for the mass percent of fluorine free polymer as hydrophobic monomer 80-95%, function monomer 5-20%；

The hydrophobic monomer has the acrylate of hydrophobic carbon chain, and hydrophobic carbon chain group can be straight chain, branch or polycyclic One or more mixing of the hydrophobic alkyl of shape；

The function monomer I is selected from one or more mixing with the monomer with quaternary ammonium salt cationic；

The function monomer II is selected from one or more mixing of the monomer with crosslinkable groups；

The function monomer III is selected from one or more mixing of the monomer of small molecule chain acrylate；

The surfactant is selected from nonionic and cationic surface active agent；

The auxiliary agent includes that pH adjusts auxiliary agent, secondary solvent.

2. free-floride cationic polyacrylate waterproofing agent according to claim 1, which is characterized in that hydrophobic monomer is selected from 10 To the mixing of the acrylate or methacrylate or above-mentioned acrylate and methacrylate of the alcohol of 24 carbon atoms Object.

3. free-floride cationic polyacrylate waterproofing agent according to claim 2, which is characterized in that contain 10 to 24 carbon The acrylate or methacrylate of the alcohol of atom are branches, or be also straight chain or it is cricoid.

4. free-floride cationic polyacrylate waterproofing agent according to claim 1, which is characterized in that with quaternary ammonium salt sun from The function monomer I of son is selected from acrylamide alkyl quaternaries cation monomer or acryloyloxyalkyl quaternaries cation list One of body is a variety of, and structure is as follows:

X=-O- ,-NH-

R₁=H-, CH₃-；R₂=-CH₂CH₂-、-CH₂CH₂CH₂-

R₃The structures such as=different carbon chain alkyl or benzyl.

5. free-floride cationic polyacrylate waterproofing agent according to claim 1, which is characterized in that cross linkable function list Body II is selected from acrylamide, Methacrylamide, hydroxyethyl methacrylate, N hydroxymethyl acrylamide, hydroxyethyl methacrylate The chloro- 2- of propyl ester, glycidyl methacrylate, hydroxy-ethyl acrylate, glycidyl acrylate, hydroxypropyl acrylate, 3- One of acrylate, 3- chlorine-2-hydroxyl propyl methacrylate or a variety of combinations.

6. free-floride cationic polyacrylate waterproofing agent according to claim 1, which is characterized in that small molecule chain acrylic acid Ester function monomer III be selected from methyl methacrylate, methyl acrylate, isobornyl methacrylate, ethyl methacrylate, N-BMA, ethyl acrylate, n-propyl, n-butyl acrylate, sec-butyl acrylate, i-butyl One of ester, acrylic acid-2-ethyl caproite, n octyl methacrylate or a variety of combinations.

7. free-floride cationic polyacrylate waterproofing agent according to claim 1, which is characterized in that the surfactant For the compound of cationic emulsifier and nonionic emulsifier；The cationic emulsifier includes but is not limited to alkylamine quaternary amines One of salt, alkyl ester based quaternary ammonium salt, alkyl acyl quaternary ammonium salt and polyoxyethylene alkyl amine quaternary ammonium salt are a variety of；It is described it is non-from Sub- emulsifier include but is not limited to straight-chain fatty alcohol polyoxyethylene ether, branched fatty alcohol polyoxyethylene ether, polyol esters of fatty acids, Aliphatic acid polyethenoxy polyol ester, polyoxyethylene carboxylate, multi-styrene phenol polyethenoxy ether and polyxyethylated sugar One of glycosides is a variety of.

8. free-floride cationic polyacrylate waterproofing agent according to claim 1, which is characterized in that the no fluoro water proofing agent PH value is between 4-7；It includes acid or alkali or amino acid that the pH, which adjusts auxiliary agent,.

9. free-floride cationic polyacrylate waterproofing agent according to claim 1, which is characterized in that the secondary solvent choosing From ethyl alcohol, acetone, isopropanol, propylene glycol, dipropylene glycol, tripropylene glycol, four propylene glycol it is one or more.

10. a kind of preparation method of floride-free cationic polyacrylate waterproofing agent as described in claim 1, which is characterized in that The following steps are included:

(1) hydrophobic monomer, 50 DEG C of boiling point or more of function monomer, surfactant, auxiliary agent and water are mixed and is emulsified, obtained pre- Lotion；

(2) the pre-emulsion 55-80 DEG C of addition initiator for reaction 2.5-8h of heating that step (1) obtains, boiling point are lower than 50 DEG C of function Monomer is added at one time or is gradually added, and system temperature is down to room temperature after reaction, obtains target product after filtering.

Technical field

The present invention relates to a kind of waterproofing agent in textile printing and dyeing field, especially a kind of floride-free cationic polyacrylate waterproof Agent, while a kind of preparation method of floride-free cationic polyacrylate waterproofing agent is additionally provided in the present invention.

Background technique

With the increasingly raising of current quality of the life, green, health, low-carbon, environmental protection new material new process be people institute The target of pursuit.With the closely bound up textile with water-proof function of people increasingly by the weight of people in daily life Depending on.Although but be mostly used in the waterproofing agent good application effect of fabric water repellent finish in the market, all contain perfluor or length Chain polyfluoro structure, the especially base class of sulphonyl containing perfluorooctane compound (PFOS) and perfluoro caprylic acid (PFOA) (i.e. perfluor C8 chemical combination Object) ingredient, this kind of fabric waterproof functional finishing agent has multiple toxins, difficult for biological degradation, so that forcing people to develop assigns spinning The novel no fluoro water proofing agent of fabric waterproofing function.

Polyacrylate high polymer is strong with preferable water resistance, solvent resistance, film forming and adhesive force, produces work The advantages that skill is simple, low in cost, using the hydrophobicity of Long carbon chain and the cross linkable of-COOH isopolarity group, by long carbon Chain acrylate monomer carries out emulsion polymerization, the emulsion-type polyacrylate of preparation with the acrylic monomer with highly polar group Class waterproofing agent has many advantages, such as at low cost, safe and non-toxic, environmentally friendly using water as continuous phase.About Long carbon chain polyacrylate without The research work of fluoro water proofing agent lotion is carried out in terms of emulsifier, monomer structure, copolymer molecule structure Modification and optimization, to improve the stability and water repellency of waterproofing agent.The particles size and distribution range of waterproof agent emulsion is to lotion Stability influence it is huge, emulsion particle diameter is excessive, can generate gelatin phenomenon, influences its service performance.

ZL201080009570.7, ZL201310505871.4, ZL201510729297.X, WO2015178471A1 report Using Long carbon chain polyacrylate with polyethylene wax nonionic surfactant and cationic surfactant synergistic effect under Preparation is without fluoro water proofing agent, and although such waterproofing agent is free from Organic fluoride, but Long carbon chain polyacrylate is object with polyethylene wax Reason is blended, and waterproofing agent stability of emulsion is undesirable, and the fabric water repellent effect after carrying out water-proofing treatment is not lasting. ZL201711292001.8 is by the metal complex of Long carbon chain carboxylic acid, cation-modified Long carbon chain amino resins, wax in cation Waterproof agent emulsion is prepared under emulsifier and nonionic emulsifier synergistic effect, is still in the water repellent systems using physical blending Method introduce wax component, although introducing Long carbon chain amino resins can be improved the emulsifying effectiveness of system, castering action has Limit, and the method for three kinds of polymer molecule physical blendings is emulsified, the waterproofing agent waterproof limited durability of preparation. Long carbon chain acrylate is carried out copolymerization system under anion emulsifier effect with cross-linking type monomer by US2017342275-A1 report Standby waterproofing agent, its crosslinker component of this kind of waterproofing agent is excessively high, be easy to cause crosslinking degree excessively high, and processed fabric is caused to occur Deformation, if needing to add a large amount of emulsifier, be easy to causeing arrangement in addition, the system will prepare stable waterproof agent emulsion Afterwards because caused by the loss of emulsifier polymer waterproof membrane relaxation occurs effect is caused gradually to decay.JP2017165872A report one Kind effective component is extended chain polypropylene acid esters, alkenyl halide polymer waterproofing agent containing 18-30C, although which has Preferable waterproof effect, but its polymer chain, with the bonding for not having chemical bond is organized between fabric, function and effect difficulty is held Long.ZL201810883529.4 is reported under cationic surfactant and nonionic surfactant effect and utilizes long-chain propylene Acid esters congenerous monomer carries out the waterproof agent emulsion that polymerization prepares core-shell structure, uses in the waterproofing agent emulsion preparation process Larger amount of surfactant, the fabric after arranging influence its water repellent because of the loss of surfactant in use The persistence of effect, and it is not environmentally friendly enough hydrophilic solvent to be added in system.

Summary of the invention

The technical problem to be solved by the present invention is to overcome deficiency in the prior art, provide a kind of novel floride-free polypropylene Acid esters waterproofing agent and preparation method thereof.This novel floride-free polyacrylate waterproofing agent be cationic surfactant and it is non-from Under sub- surfactant synergistic effect, by long chain acrylate, quaternary ammonium salt cationic monomer, functional monomer, cross-linking type monomer Solid content made of copolymerization is high, partial size is small and the polymer emulsion of stable homogeneous, to assign the excellent water repellency of fabric, antibacterial The performances such as property, durability.

To achieve the goals above, a kind of floride-free cationic polyacrylate waterproofing agent designed by the present invention, wherein each Component and mass percent are as follows:

Fluorine free polymer 20%-30%, surfactant 1-4%, auxiliary agent 0.25-2.5%, surplus are water；

The fluorine free polymer is formed by hydrophobic monomer and function monomer I-III by free radical polymerization, the hydrophobic monomer The mass percent for accounting for fluorine free polymer with function monomer is hydrophobic monomer 80-95%, function monomer 5-20%；

The hydrophobic monomer is selected from 10 to 24 carbon atoms, preferably 12 to 24 carbon atoms, and more preferable 16 to 24 carbon The acrylate or methacrylate of the alcohol of atom or the mixture of this acrylate and methacrylate；

The acrylate or methacrylate for the alcohol that the hydrophobic monomer contains 10 to 24 carbon atoms are branches, or Be also straight chain or it is cricoid；

The function monomer I with quaternary ammonium salt cationic is selected from acrylamide alkyl quaternaries cation monomer or third One of alkene acyloxyalkyl group quaternaries cation monomer is a variety of, and structure is as follows:

X=-O- ,-NH-

R₁=H-, CH₃-；R₂=-CH₂CH₂-、-CH₂CH₂CH₂-

R₃The structures such as=different carbon chain alkyl or benzyl

The cross linkable function monomer II is selected from acrylamide, Methacrylamide, hydroxyethyl methacrylate, N- hydroxyl Methacrylamide, hydroxy propyl methacrylate, glycidyl methacrylate, hydroxy-ethyl acrylate, acrylic acid shrink sweet One of grease, hydroxypropyl acrylate, 3- chlorine-2-hydroxyl propyl acrylate, 3- chlorine-2-hydroxyl propyl methacrylate Or a variety of combination；

The small molecule chain acrylate functional monomer III is selected from methyl methacrylate, methyl acrylate, metering system The positive fourth of sour isobornyl thiocyanoacetate, ethyl methacrylate, n-BMA, ethyl acrylate, n-propyl, acrylic acid One of ester, sec-butyl acrylate, isobutyl acrylate, acrylic acid-2-ethyl caproite, n octyl methacrylate are a variety of Combination；

The surfactant is the compound of cationic emulsifier and nonionic emulsifier；

The cationic emulsifier includes but is not limited to alkylamine quaternary amines salt, alkyl ester based quaternary ammonium salt, alkyl acyl quaternary ammonium One of salt and polyoxyethylene alkyl amine quaternary ammonium salt are a variety of；

The nonionic emulsifier includes but is not limited to straight-chain fatty alcohol polyoxyethylene ether, branched fatty alcohol polyoxyethylene Ether, polyol esters of fatty acids, aliphatic acid polyethenoxy polyol ester, polyoxyethylene carboxylate, multi-styrene phenol polyethenoxy One of ether and polyxyethylated glucosides are a variety of.

The adjusting auxiliary agent includes acid or alkali or amino acid, and no fluoro water proofing agent pH value is between 4-7.

The secondary solvent be selected from ethyl alcohol, acetone, isopropanol, propylene glycol, dipropylene glycol, tripropylene glycol, 4 the third two Alcohol it is one or more.

The initiator is selected from one of persulfate, oil-soluble azo-initiator or water-soluble azo class initiator Or it is a variety of.Including but not limited to one of ammonium persulfate, azodiisobutyronitrile, azobisisobutryamide chloride or a variety of.

A kind of preparation method of free-floride cationic polyacrylate waterproofing agent, comprising the following steps:

(1) hydrophobic monomer, 50 DEG C of boiling point or more of function monomer, surfactant, auxiliary agent and water are mixed and is emulsified, obtained To pre-emulsion；

(2) the pre-emulsion 55-80 DEG C of addition initiator for reaction 2.5-8h of heating that step (1) obtains, boiling point are lower than 50 DEG C Function monomer is added at one time or is gradually added, and system temperature is down to room temperature after reaction, obtains target after filtering Product.

Monomer containing quaternary ammonium salt cationic structure is carried out copolyreaction with Long carbon chain acrylate by the present invention, due to season In the charge dispersibility of ammonium salt cationic monomer and newly-generated copolymer molecule chain due to introducing quaternary ammonium salt cationic structure The self-emulsifying being endowed, the emulsifying effectiveness of the polymer emulsion generated when improving polymerization reaction, to improve copolymer cream The stability and dispersibility of liquid.The floride-free cationic polyacrylate waterproofing agent solid content that the present invention develops is high, partial size is small and equal One stablizes, water repellency is excellent.Quaternary ammonium salt cationic structural chain section is bonded on waterproofness copolymer molecule, intrinsic strong pole Property and antibiotic property, to improve its waterproof durability and antibacterial to fabric processed, especially cellulose family, protein-based fabric Property.

Compared with prior art, advantages of the present invention:

Quaternary ammonium salt cationic group is introduced in floride-free extended chain polypropylene esters of gallic acid waterproofing agent macromolecular chain, imparting is developed Waterproofing agent emulsion solid content is high, partial size is small and distribution stable homogeneous, can assign the excellent water repellency of textile, is water permeability resistance, resistance to Long property, antibiotic property etc..

Specific embodiment

In order to verify the waterproof effect of the textile after floride-free waterproofing agent treatment of the present invention, can by standard method into Row is investigated, to compare.The standard method is that waterproof effect is investigated using national standard GB 4745-2012, and here is method letter It is situated between.

National standard " GB 4745-2012 " test method:

The sample for intercepting 18 × 18cm, is compressed, and be installed on the firm banking being at an angle of 45 degrees to the horizontal plane with clamper, is used The distilled water or deionized water of 250mL (20 ± 2 DEG C) is rapidly and smoothly in hopper, by being located at sample overcentre Spray head averagely continuously sprays in 25~30s, towards sample center.Spray finishes, and rapidly takes away clamper, makes to try The sample level of facing down into is lightly patted, is then rotated, and the sample level of facing up into is made, and is lightly patted, Sample wetness degree is observed, is compareed with verbal description and with picture and evaluates its grade, take 2 average values.

Rating scale text are as follows:

0 grade-entire specimen surface complete wetting.

1 grade-by leaching surface complete wetting.

Beyond soaking at spray point, wetting areas exceeds by leaching surface half 1-2 grades-specimen surface.

2 grades-specimen surface at spray point beyond soaking, and wetting areas is about by leaching surface half.

Beyond soaking at spray point, wetting areas is less than by leaching surface half 2-3 grades-specimen surface.

It is soaked at 3 grades-specimen surface spray point.

3-4 grades-specimen surface, which is equal to or less than at the spray point of half, to be soaked.

4 grades-specimen surface has to be soaked at fragmentary spray point.

4-5 grades-specimen surface does not soak, and has a small amount of droplet.

5 grades-specimen surface does not have droplet or wetting.

The effect of sample after washing is also investigated, washing conditions are standard synthetic detergent 1g/L, washing machine bath raio 1: 30 washings, rinse, dehydration, the drying of 100 DEG C × 3min forming machine.