WO2020155292A1 - 一种利用侧链双键制备的聚氨酯-丙烯酸酯类拒水剂 - Google Patents

一种利用侧链双键制备的聚氨酯-丙烯酸酯类拒水剂 Download PDF

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WO2020155292A1
WO2020155292A1 PCT/CN2019/077205 CN2019077205W WO2020155292A1 WO 2020155292 A1 WO2020155292 A1 WO 2020155292A1 CN 2019077205 W CN2019077205 W CN 2019077205W WO 2020155292 A1 WO2020155292 A1 WO 2020155292A1
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carbon
polyurethane
acrylate
double bonds
carbon double
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French (fr)
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杜金梅
王少飞
许长海
姚安康
周攀飞
逢赠媛
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Jiangnan University
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Jiangnan University
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    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
    • D06M15/00—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment
    • D06M15/19—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment with synthetic macromolecular compounds
    • D06M15/37—Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
    • D06M15/564—Polyureas, polyurethanes or other polymers having ureide or urethane links; Precondensation products forming them
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
    • D06M2200/00—Functionality of the treatment composition and/or properties imparted to the textile material
    • D06M2200/10—Repellency against liquids
    • D06M2200/12—Hydrophobic properties

Definitions

  • the invention relates to a polyurethane-acrylate water repellent prepared by using side chain double bonds, and belongs to the technical field of environmentally friendly polymers.
  • Water-repellent textiles are a kind of functional textiles, which are waterproof, stain-proof and self-cleaning.
  • the surface of the fabric after the water-repellent finishing cannot be wetted by water, but it still maintains the moisture permeability of the fabric and meets the requirements of wearing .
  • the fluorine element has a low surface energy and has the effect of repelling oil while repelling water.
  • fluorine-containing compounds In use, it is difficult to be wetted or adhered by various liquids, and has high thermal and chemical stability. Although fluorine-containing compounds have the characteristics of low concentration and high efficiency, they are costly and affect the shade of fabrics during washing. Moreover, as environmental protection has become more and more important, the world is banning the inclusion of perfluorooctanoate (PFOA) and perfluorooctane. As a waterproofing agent for sulfonyl compounds (PFOS), fluorine-free waterproofing agents are strongly recommended. Therefore, it is the current international development trend to develop non-toxic, low VOC content, and environmentally friendly fluorine-free water repellents to replace the current fluorine-containing water repellents.
  • PFOA perfluorooctanoate
  • PFOS perfluorooctane
  • Water-based polyurethane has the advantages of non-flammability, low cost, and environmental protection, and has been widely used in water-based inks, coatings, adhesives, leather finishing agents and other fields.
  • water-based polyurethane has disadvantages such as poor water resistance, low gloss fastness, and high price, which limit its wide application.
  • researchers mostly use acrylic monomers and polyurethane graft modification to prepare water repellents.
  • chemical modification methods are mostly used to combine the waterborne polyurethane and acrylic monomers by chemical bonds to improve their fastness .
  • the most commonly used method to introduce active double bonds into its molecular chain is to add monohydroxy unsaturated organics, such as hydroxymethyl acrylate and hydroxyethyl acrylate, after the polyurethane prepolymer is formed.
  • Etc. using the hydroxyl group contained in the prepolymer to cap the terminal isocyanate group, that is, introducing a carbon-carbon double bond at the end of the macromolecular segment; another method is to introduce a carbon-carbon double bond inside the polyurethane molecular segment, adding Unsaturated organic compounds containing active hydroxyl groups at both ends, such as ethylene glycol, butenediol, 3-hexene-1,6-diol, etc., using active hydroxyl groups to introduce the above monomers into the macromolecule in the form of chain extension Chain segment.
  • Unsaturated organic compounds containing active hydroxyl groups at both ends such as ethylene glycol, butenediol, 3-hexene-1,6-diol, etc.
  • the above two methods of introducing carbon-carbon double bonds have solved the problem of poor polyurethane/acrylate compatibility to a certain extent, but they also have major drawbacks.
  • the former method of introducing carbon-carbon double bonds is located at the end of the polyurethane segment.
  • the isocyanate group has been partially blocked, so it is difficult to obtain a polyurethane molecule with a larger average molecular weight.
  • the restriction of the molecular structure results in only two active double bonds on the polyurethane molecule obtained, which makes the access to acrylic acid
  • the number of ester monomers is limited.
  • the present invention introduces carbon-carbon double bonds in the side chain of the polyurethane molecule through the dihydroxy small molecule chain extender (formula II) containing carbon-carbon double bonds, and introduces more carbon-carbon double bonds while increasing the molecular weight.
  • the carbon-carbon double bond of the side chain is exposed at the outer end, which facilitates free radical polymerization with the double bond of the acrylate monomer.
  • the present invention uses oxime organic compounds to block the exposed isocyanate at the end of the polyurethane prepolymer, and the unblocking reaction can occur at a certain temperature.
  • the isocyanate released during the baking process reacts with other groups containing active hydrogen and the fabric to establish the cross-linking between polymer molecules and the fabric The chemical bond between them gives the product higher fastness.
  • the first object of the present invention is to provide a polyurethane-acrylate water-repellent agent which introduces a carbon-carbon double bond in the side chain of the polyurethane, and its structural formula is as shown in formula (I):
  • R 1 is an oxime-type blocking agent
  • R 2 is a diisocyanate monomer
  • R 3 is selected from alkyl, phenyl, cyclic, acyl, ester, carbonyl, and ether groups with any number of carbon atoms
  • R 4 Selected from alkyl, cyclic group and its derivatives, phenyl and its derivatives
  • R 5 is a carbon chain with 1-18 carbon atoms
  • R 6 is polyether or polyol polyorganic compound
  • R 7 is hydrophilic Sexual chain extender
  • a and n are natural numbers from 1-100.
  • R 1 is a structural unit of an oxime blocking agent
  • R 2 is a diisocyanate monomer containing an aliphatic or aromatic structural unit
  • R 3 is selected from an alkyl group with any number of carbon atoms, Phenyl, cyclic, acyl, ester, carbonyl, ether
  • R 4 is selected from alkyl, cyclic and its derivatives, phenyl and its derivatives
  • R 5 is a carbon chain with 1-18 carbon atoms
  • R 6 is a polyether or polyol polyorganic compound structural unit
  • R 7 is a hydrophilic chain extender structural unit
  • a, n are natural numbers from 1-100.
  • the second object of the present invention is to provide a preparation method of the above polyurethane-acrylate water repellent, the method comprising:
  • the polyurethane prepolymer, the dihydroxy small molecule chain extender containing double carbon-carbon double bonds, and the remaining hydrophilic chain extender continue to react for a period of time to obtain an aqueous polyurethane emulsion containing carbon-carbon double bonds in the side chain;
  • the dihydroxy small molecule chain extender with double carbon-carbon double bond is a compound represented by formula (II);
  • R 3 is selected from alkyl groups, phenyl groups, cyclic groups, acyl groups, ester groups, carbonyl groups, and ether groups with any number of carbon atoms
  • R 4 is selected from alkyl groups, cyclic groups and derivatives thereof, phenyl groups and derivatives thereof .
  • the dihydroxy small molecule chain extender containing carbon-carbon double bonds includes any one or more of the following mixtures: 7-octene-1,2-diol, pentaerythritol Diacrylate, 6-heptene-2,4-diol, 3-allyloxy-1,2-propanediol, glycerol methacrylate (GM), trimethylolpropane monoallyl ether, 2 ,2-bishydroxymethylbutanoic acid-3-hydroxy-2-(2-methacryloxy)-propyl ester, 2-(3-isocyanatomethyl)-3,5,5-tri Methylcyclohexylcarbamoyloxy) ethyl acrylate.
  • 7-octene-1,2-diol pentaerythritol Diacrylate
  • 6-heptene-2,4-diol 3-allyloxy-1,2-propanediol
  • glycerol methacrylate (GM) tri
  • the molar ratio of isocyanate to hydroxyl of the polyurethane prepolymer in the step (1) is 1.1-1.7.
  • the hydrophilic chain extender agent in the step (1) accounts for 4% to 11% of the total mass of the monomer.
  • the dihydroxy small molecule chain extender containing carbon-carbon double bonds in the step (2) accounts for 1%-10% of the total monomer mass.
  • the molar ratio of the blocking agent to the unreacted isocyanate in the step (3) is 1.5-2.
  • the degree of neutralization in the step (4) is 80%-100%.
  • the step (5) is obtained by adding water and self-emulsifying by stirring according to the solid content of 20%-40%.
  • the mass ratio of the acrylate monomer and the side chain carbon-carbon double bond-containing polyurethane self-emulsion solid content is (1 ⁇ 4):1.
  • the acrylate monomer in the step (6), is an acrylate having an ester group with 1-18 carbon atoms.
  • the step (6) is to add the acrylate monomer into the aqueous polyurethane emulsion, stir and emulsify for a period of time, and then add an initiator to polymerize to obtain a polyurethane-acrylate water repellent.
  • the diisocyanate includes any one or more of the following mixtures: isophorone diisocyanate, toluene diisocyanate, xylylene diisocyanate, hexamethylene diisocyanate Isocyanate, xylylene diisocyanate, dicyclohexylmethane diisocyanate, 4,4-diphenylmethane diisocyanate, lysine diisocyanate, 1,5-naphthalene diisocyanate, trimethylhexamethylene Methyl diisocyanate, dodecylbenzene-2,4-diisocyanate, p-phenylene diisocyanate, m-phenylene diisocyanate, diphenylmethane diisocyanate, dicyclohexylmethane diisocyanate.
  • the polymer polyol includes one or a mixture of polyether polyols and polyester polyols with a molecular weight of 300 to 2000: polytetrahydrofuran glycol, polyhexamethylene glycol Ethylene glycol ester diol, polyglycol sebacate diol, poly-1,4-butanediol adipate diol, poly- ⁇ -caprolactone diol, polypropylene glycol, polyethylene Diol, polycarbonate diol, polybutadiene diol, acrylic polyol.
  • the hydrophilic chain extender includes any one or more of the following mixed 2,2-dimethylolbutanoic acid and 2,2-dimethylolpropionic acid , N-methyldiethanolamine, diethylenetriamine, triethanolamine, tartaric acid, dihydroxy half ester, dimethylolpropionic acid, dihydroxy half ester, methyldiethanolamine, sodium ethylenediaminoethanesulfonate.
  • the capping agent includes any one or a mixture of the following: butanone oxime, butamidine oxime, acetoxime, methyl ethyl ketoxime, formaldehyde oxime, bromophenol oxime, cyclohexanone Oxime, n-heptanaldoxime, dimethylglyoxime, tetramethylcyclobutanedione monooxime.
  • the neutralizer includes one or more of triethylamine, ammonia, sodium hydroxide, hydrochloric acid, acetic acid, N,N-dimethylethanolamine, diethanolamine, and triethanolamine mixing.
  • the preparation method of the polyurethane prepolymer in the step (1) shown specifically includes:
  • the polymer polyol (accounting for 79%-95% of the total monomer mass), hydrophilic chain extender (accounting for 4%-11% of the total monomer mass), and dihydroxy small molecules containing carbon-carbon double bonds
  • the chain agent (accounting for 1%-10% of the total mass of the monomers) is vacuum dried at 80-90°C to produce water for 3 to 4 hours.
  • isocyanate According to the ratio of isocyanate to hydroxyl in 1.1 ⁇ 1.7, take part of hydrophilic chain extender (accounting for 30%-40% of the total amount of hydrophilic chain extender), polymer polyol, and add dibutyltin dilaurate ( (Accounting for 0.08% of the total monomer mass involved in the reaction), diisocyanate was added dropwise under nitrogen protection, temperature 70 ⁇ 80°C, and di-n-butylamine method was used to determine the -NCO% value in the reaction system to reach the theoretical value and proceed to the next step ( The theoretical residual amount of isocyanate ⁇ 32 ⁇ 36%).
  • the step (2) specifically includes:
  • the step (3) specifically includes:
  • the steps (4) and (5) specifically include:
  • the step (6) specifically includes:
  • the third object of the present invention is to prepare a hydrophobic fabric comprising the above-mentioned polyurethane-acrylate water repellent.
  • the preparation process of the hydrophobic fabric includes: using a rolling-drying-baking process, the fabric has a rolling-over rate of 70-150%, a padding concentration of 20-180g/L, and a water repellent After the emulsion is pre-baked at 60-100°C for 1-5min, and baked at 120-160°C for 1-5min.
  • the present invention introduces the carbon-carbon double bond into the side chain of the polyurethane macromolecule through the dihydroxy small molecule chain extender containing carbon-carbon double bond (formula II), and utilizes the active double bond on the side chain of the polyurethane and the acrylic monomer Free radical polymerization occurs to prepare polyurethane-acrylate water repellent. While introducing more active double bonds, a larger molecular weight polyurethane is obtained, which increases the number of acrylate monomers involved in the grafting reaction and covers the side ends of the polyurethane molecular chain, avoiding the entanglement of the macromolecular chain polyurethane on the main chain of the polyurethane molecule. The activity of the carbon-carbon double bond is reduced, the content of hydrophobic groups in the molecular chain is increased, a branched structure is produced, the compatibility of polyurethane/acrylate is improved, and a water repellent with stable performance is obtained.
  • the present invention uses non-toxic, low VOC content, environmentally friendly water-based polyurethane as an emulsifier and acrylate monomer to prepare a water repellent, and uses an oxime organic compound to block the isocyanate of the polyurethane at the end of the polyurethane.
  • the unblocking reaction occurs at a certain temperature, which makes the exposed isocyanate react with the active hydrogen group on the fabric, and the water repellent and the fabric are cross-linked through chemical bonds, which solves the fluorine-containing water repellent environment
  • the pollution problem and the poor washing fastness of long carbon chain water repellent make the contact angle of the fabric as high as 152° or more, and the static water contact angle of the fabric after 25 household washing machine washing is higher than 140°.
  • Figure 1 The static water contact angle diagram of the treated fabric.
  • the isophorone diisocyanate was slowly added dropwise to containing polytetrahydrofuran and 30% 2,2-dimethylol Butyric acid (the molar ratio of isocyanate to hydroxyl is 1.1, 1.2, 1.3, 1.4, 1.5, 1.6, 1.7, respectively), the reaction temperature is 80°C, and the -NCO content in the reaction system is determined by the di-n-butylamine method after reaching the theoretical value Proceed to the next step (theoretical remaining isocyanate ⁇ 32%).
  • the fabric has a rolling-over rate of 70%, a padding concentration of 180g/L, and the water repellent emulsion is pre-baked at 100°C for 3min and baked at 140°C for 3min.
  • the related parameters of the treated fabric are shown in Table 1.
  • Table 1 The performance of water repellent prepared with different isocyanate to hydroxyl molar ratio
  • the washing resistance test is carried out according to the 2A test standard in AATCC Test Method 61-2010 "Color Fastness to Washing".
  • AATCC 2A standard is equivalent to 5 washings of ordinary household washing machines; in the ratio of isocyanate to hydroxyl At 1.1, the prepolymer is not easy to emulsify, and the polyurethane prepolymer terminated with isocyanate is obtained; when the ratio is 1.7, the molecular weight of the polyurethane prepolymer is too large, the residual -NCO content in the system increases, and the water emulsification is more generated Strong urea-based water repellency, too large emulsion particle size, poor storage stability.
  • Product hydrophobic effect Comparing the polyurethane acrylate water repellent prepared under different ratios, when the ratio is 1.1 or 1.7, the prepared polyurethane emulsion is unstable and cannot effectively undergo free radical polymerization with acrylic monomers. When the ratio is 1.2-1.6, the water repellent is stable, the water repellent effect is better, and it has good anti-pilling performance.
  • polyurethane self-emulsion the molar ratio of isocyanate to hydroxyl group was selected to be 1.3, and other conditions were referred to Example 1, to prepare a polyurethane self-emulsion.
  • WPUA polyurethane-acrylate water repellent
  • the fabric has a rolling-over rate of 70%, a padding concentration of 180g/L, and the water repellent emulsion is pre-baked at 100°C for 3min and baked at 140°C for 3min. See Table 2 for the relevant parameters of the treated fabric.
  • washing resistance test is carried out according to the 2A test standard in AATCC Test Method 61-2010 "Color Fastness to Washing".
  • AATCC 2A standard is equivalent to 5 washings of ordinary household washing machines.
  • the fabric has a rolling-over rate of 150%, a padding concentration of 20g/L, and the water repellent emulsion is pre-baked at 60°C for 5 minutes and baked at 160°C for 1 minute.
  • the relevant parameters of the treated fabric are shown in Table 3.
  • diphenylmethane diisocyanate was slowly added dropwise to the poly- ⁇ -caprolactone diol and 30% of the two Methylolpropionic acid (the molar ratio of isocyanate to hydroxyl is 1.3), the reaction temperature is 75°C, the di-n-butylamine method is used to determine the -NCO content in the reaction system to reach the theoretical value, and then proceed to the next step (theoretical remaining isocyanate ⁇ 32%);
  • the fabric has a rolling-over rate of 100%, a padding concentration of 120g/L, and the water repellent emulsion is pre-baked at 90°C for 3min and baked at 140°C for 2min.
  • the relevant parameters of the treated fabric are shown in Table 3.
  • the mass ratio of solids is 2:1)
  • An azobisisobutyronitrile initiator (0.6% of the total mass of the acrylate monomer) was added dropwise, and the temperature was lowered after being kept for 2 hours, and the material was discharged to obtain a polyurethane-acrylate water repellent (WPUA).
  • WPUA polyurethane-acrylate water repellent
  • the fabric has a rolling-over rate of 80%, a padding concentration of 160g/L, and the water repellent emulsion is pre-baked at 70°C for 5 minutes and baked at 150°C for 4 minutes.
  • the relevant parameters of the treated fabric are shown in Table 3.
  • the molar ratio to the hydroxyl group is 1.3
  • the reaction temperature is 70°C
  • the -NCO content in the reaction system is determined by the di-n-butylamine method to reach the theoretical value, and then proceed to the next step (theoretical remaining isocyanate ⁇ 32%).
  • the fabric has a rolling-over rate of 70%, a padding concentration of 180g/L, and the water repellent emulsion is pre-baked at 60°C for 5 minutes and baked at 150°C for 2 minutes.
  • the relevant parameters of the treated fabric are shown in Table 3.
  • the isophorone diisocyanate was slowly added dropwise to containing polytetrahydrofuran and 30% 2,2-dimethylol Butyric acid (the molar ratio of isocyanate to hydroxyl is 1.3), the reaction temperature is 80°C, and the -NCO content in the reaction system is determined by the di-n-butylamine method to reach the theoretical value, and then proceed to the next step (theoretical remaining isocyanate ⁇ 32% ).
  • the fabric has a rolling-over rate of 70%, a padding concentration of 180g/L, and the water repellent emulsion is pre-baked at 100°C for 3min and baked at 140°C for 3min.
  • the relevant parameters of the treated fabric are shown in Table 3.
  • the isophorone diisocyanate was slowly added dropwise to containing polytetrahydrofuran and 30% 2,2-dimethylol Butyric acid (the molar ratio of isocyanate to hydroxyl is 1.3), the reaction temperature is 80°C, and the -NCO content in the reaction system is determined by the di-n-butylamine method to reach the theoretical value, and then proceed to the next step (theoretical remaining isocyanate ⁇ 32% ).
  • the fabric has a rolling-over rate of 70%, a padding concentration of 180g/L, and the water repellent emulsion is pre-baked at 100°C for 3min and baked at 140°C for 3min.
  • the relevant parameters of the treated fabric are shown in Table 3.
  • washing resistance test is carried out according to the 2A test standard in AATCC Test Method 61-2010 "Color Fastness to Washing".
  • AATCC 2A standard is equivalent to 5 washings of ordinary household washing machines.
  • the present invention uses a double-carbon double bond-containing dihydroxy small molecule chain extender to introduce carbon-carbon double bonds in the side chain of the polyurethane (Examples 1-6), and the introduction of carbon-carbon double bonds at the end of the polyurethane (Comparative Example) 1) Compared with the introduction of carbon-carbon double bonds in the polyurethane main chain (Comparative Example 2, Comparative Example 3), the water-repellent agent prepared according to the steps of Examples 1-6 is more stable, and the finished fabric has a better water-repellent effect and good performance Anti-pilling performance.
  • Product washing fastness The polyurethane acrylate water repellent prepared in comparative examples 1-6 under different acrylate monomer ratios, the static water contact angle (hydrophobicity) of the fabrics after 25 times of household washing machine washing is higher than 142°, with higher hydrophobicity, indicating that the fabric finished with the water repellent prepared by the present invention has higher fastness to washing.
  • Comparative Examples 1-6 prepared polyurethane acrylate water repellents under different acrylate monomer ratios, after 10 batches of finishing, the range error of the static water contact angle of each finishing fabric is ⁇ 1°, it can be seen from the contact angle data that the hydrophobic effect of the fabric has good repeatability.

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Abstract

本发明公开了一种利用侧链双键制备的聚氨酯-丙烯酸酯类拒水剂，属于环保型高分子技术领域。本发明利用具有碳链结构的含碳碳双键的双羟基小分子扩链剂在聚氨酯侧链引入碳碳双键，调节水性聚氨酯链段上与丙烯酸酯单体参与自由基聚合的双键数目，产生支化结构，改善聚氨酯与丙烯酸酯相容性；通过肟类封端结构与织物结合，增加织物牢度。经本发明制备的聚氨酯-丙烯酸酯类拒水剂无毒、低VOC，整理后织物的物理、化学性能明显改善，有较好应用前景。

Description

一种利用侧链双键制备的聚氨酯-丙烯酸酯类拒水剂 技术领域
本发明涉及一种利用侧链双键制备的聚氨酯-丙烯酸酯类拒水剂，属于环保型高分子技术领域。
背景技术
随着社会的发展进步，在纺织品的应用中，人们对纺织品的服用性能要求越来越高，不仅仅限于穿着舒适性，还要具备拒水、防紫外、阻燃等功能，因此功能纺织品的研究发展越来越受到人们的关注。拒水纺织品属于功能纺织品的一种，具备防水、防污及自清洁功能，经拒水整理后的织物表面不能被水所润湿，但仍保持了织物的透湿透气性能，达到服用要求。氟元素具有较低的表面能，在拒水的同时还有拒油的作用。在使用时，难于被各种液体润湿或附着，具有较高的热稳定性和化学稳定性。含氟化合物虽具有低浓高效的特质，但是成本较高，洗涤时会影响织物的色光，而且随着环境保护越来越受重视，全球正全面禁止含有全氟辛酸铵(PFOA)、全氟辛烷磺酰基化合物(PFOS)的防水剂，大力推荐无氟防水剂。因此研发无毒、低VOC含量、对环境友好的无氟拒水剂以替代目前的含氟类拒水剂已是当前国际上的发展趋势。
水性聚氨酯(WPU)具有不易燃烧、成本低、环保等优点，已广泛应用于水性油墨、涂料、胶黏剂、皮革涂饰剂等领域。然而水性聚氨酯存在耐水性差、光泽牢度低、价格昂贵等缺点，限制了其广泛的应用。科研人员多采用丙烯酸酯类单体与聚氨酯接枝改性制备拒水剂。在制备聚氨酯/丙烯酸酯拒水剂中，由于聚合物中两种组分相容性较差，大多采用化学改性的方法，将水性聚氨酯和丙烯酸酯类单体以化学键结合，提高其牢度。目前多采用向聚氨酯大分子链段末端引入活性双键，再与丙烯酸酯单体发生自由基聚合，从而改善聚氨酯/丙烯酸酯组分的相容性。根据聚氨酯异氰酸根的反应特性，向其分子链段上引入活性双键最常用的方法是在形成聚氨酯预聚体后，加入单羟基的不饱和有机物，如丙烯酸羟甲酯、丙烯酸羟乙酯等，利用其含有的羟基对预聚物的端异氰酸酯基团封端，即在大分子链段末端引入碳碳双键；另一种方法是在聚氨酯分子链段内部引入碳碳双键，加入两端含活泼羟基的不饱和有机化合物，如乙烯二醇、丁烯二醇、3-己烯-1,6-二醇等，利用活泼羟基将上述单体以扩链的形式引入到大分子链段上。
上述两种引入碳碳双键的方法，在一定程度上解决了聚氨酯/丙烯酸酯相容性差的问题，但是同样存在很大弊端，前者引入碳碳双键的方法位于聚氨酯链段的末端，由于异氰酸根基 团已经被部分封端，因此较难获得较大平均分子量的聚氨酯分子，同时分子结构的限制，导致获得的聚氨酯分子上最多只能获得两个活性双键，使得接入的丙烯酸酯单体的数量有限。后者虽在引入更多活性双键的同时在一定程度上获得较大分子量聚氨酯，改善了聚氨酯/丙烯酸酯的相容性，但较大分子量的聚氨酯分子链会使得碳碳双键活性降低，与丙烯酸酯单体不易发生接枝聚合。因此，开发一种新型大分子且双键活性高的拒水剂是有迫切需求的。
发明内容
针对上述问题，本发明通过含碳碳双键的双羟基小分子扩链剂(式Ⅱ)，在聚氨酯分子侧链引入碳碳双键，在增加分子量的同时引入更多的碳碳双键，使得侧链的碳碳双键裸露在外端，便于与丙烯酸酯单体的双键发生自由基聚合。为解决传统拒水剂耐水洗牢度差的问题，本发明采用肟类有机化合物对聚氨酯预聚体末端裸露的异氰酸根封端，可在一定温度下发生解封闭反应。经本发明制备的拒水剂整理后的织物，在焙烘过程中释放出的异氰酸根与含活泼氢的其他基团及织物发生化学反应，建立了聚合物分子间的交联及与织物之间的化学键，赋予产品较高的牢度。
本发明的第一个目的是提供一种聚氨酯-丙烯酸酯类拒水剂，所述拒水剂是在聚氨酯侧链引入碳碳双键，其结构式如式(I)所示：
Figure PCTCN2019077205-appb-000001
其中，R 1为肟类封端剂；R 2为二异氰酸酯单体，；R 3选自任意碳原子数的烷基、苯基、环基、酰基、酯基、羰基、醚基；R 4选自烷基、环基及其衍生物、苯基及其衍生物；R 5为碳原子个数1-18的碳链；R 6为聚醚或聚醇多元有机化物；R 7为亲水性扩链剂；a，n为1-100的自然数。
在本发明的一种实施方式中，R 1为肟类封端剂结构单元；R 2为二异氰酸酯单体中含脂肪族或芳香族结构单元；R 3选自任意碳原子数的烷基、苯基、环基、酰基、酯基、羰基、醚基；R 4选自烷基、环基及其衍生物、苯基及其衍生物；R 5为碳原子个数1-18的碳链；R 6为聚醚或聚醇多元有机化物结构单元；R 7为亲水性扩链剂结构单元；a，n为1-100的自然数。
本发明的第二个目的是提供上述聚氨酯-丙烯酸酯类拒水剂的制备方法，所述方法包括：
(1)利用二异氰酸酯、部分亲水性扩链剂和聚合物多元醇制备聚氨酯预聚体；
(2)聚氨酯预聚体与含双碳碳双键的双羟基小分子扩链剂、剩余亲水性扩链剂继续反应一段时间得到侧链含有碳碳双键的水性聚氨酯乳液；所述含双碳碳双键的双羟基小分子扩链剂为式(II)所示化合物；
(3)加入肟类封端剂，对异氰酸根封端(NCO％≤0.5％)；
(4)降温，加入中和剂调节pH＝7～8.5；
(5)加入去离子水进行乳化得到侧链含碳碳双键的水性聚氨酯乳液；
(6)将侧链含碳碳双键的聚氨酯乳液与丙烯酸酯类单体在引发剂条件下自由基聚合，得到聚氨酯-丙烯酸酯类拒水剂；
Figure PCTCN2019077205-appb-000002
其中，R 3选自任意碳原子数的烷基、苯基、环基、酰基、酯基、羰基、醚基；R 4选自烷基、环基及其衍生物、苯基及其衍生物。
在本发明的一种实施方式中，所述含碳碳双键的双羟基小分子扩链剂包括以下任意一种或多种的混合：、7-辛烯-1,2-二醇、季戊四醇二丙烯酸酯、6-庚烯-2,4-二醇、3-烯丙氧基-1,2-丙二醇、甲基丙烯酸甘油酯(GM)、三羟甲基丙烷单烯丙基醚、2,2-双羟基甲基丁酸-3-羟基-2-(2-甲基丙烯酰氧基)-丙酯、2-(3-异氰酸根合甲基)-3,5,5-三甲基环己基氨基甲酰基氧)丙烯酸乙酯。
本发明的一种实施方式中，所述步骤(1)中聚氨酯预聚体的异氰酸根与羟基的摩尔比值为1.1～1.7。
本发明的一种实施方式中，所述步骤(1)中亲水性扩链法剂占单体总质量的4％～11％。
本发明的一种实施方式中，所述步骤(2)中的含碳碳双键的双羟基小分子扩链剂占单体总质量的1％～10％。
本发明的一种实施方式中，所述步骤(3)中的封端剂与未反应的异氰酸根的摩尔比值为1.5～2。
本发明的一种实施方式中，所述步骤(4)中的中和度为80％～100％。
本发明的一种实施方式中，所述步骤(5)加水自乳化按照固含量20％～40％搅拌而得。
本发明的一种实施方式中，所述步骤(6)中丙烯酸酯单体与侧链含碳碳双键的聚氨酯自乳液中含固量的质量比为(1～4):1。
本发明的一种实施方式中，所述步骤(6)中丙烯酸酯单体为酯基碳原子数1-18的丙烯酸酯。
本发明的一种实施方式中，所述步骤(6)是将丙烯酸酯单体加入到水性聚氨酯乳液内，搅拌乳化一段时间后，加入引发剂聚合得到聚氨酯-丙烯酸酯类拒水剂。
在本发明的一种实施方式中，所述的二异氰酸酯包括以下任意一种或多种的混合：异氟尔酮二异氰酸酯、甲苯二异氰酸酯、苯二亚甲基二异氰酸酯、六次甲基二异氰酸酯、苯二亚甲基二异氰酸醋、二环己基甲烷二异氰酸酯、4,4-二苯基甲烷二异氰酸酯、赖氨酸二异氰酸酯、1,5-萘二异氰酸酯、三甲基六亚甲基二异氰酸酯、十二烷基苯-2,4-二异氰酸酯、对苯二异氰酸酯、间苯二异氰酸酯、二苯基甲烷二异氰酸酯、二环己基甲烷二异氰酸酯。
在本发明的一种实施方式中，所述的聚合物多元醇包括分子量为300～2000的聚醚多元醇、聚酯多元醇的一种或几种的混合：聚四氢呋喃二醇、聚己二酸乙二醇酯二醇、聚癸二酸二元醇酯二醇、聚己二酸-1,4-丁二醇酯二醇、聚-ε-己内酯二醇、聚丙二醇、聚乙二醇、聚碳酸酯二醇、聚丁二烯二醇、丙烯酸酯多元醇。
在本发明的一种实施方式中，所述亲水性扩链剂包括以下任意的一种或几种的混合2,2-二羟甲基丁酸、2,2-二羟甲基丙酸、N-甲基二乙醇胺、二乙烯三胺、三乙醇胺、酒石酸、二羟基半酯、二羟甲基丙酸、二羟基半酯、甲基二乙醇胺、乙二胺基乙磺酸钠。
在本发明的一种实施方式中，所述封端剂包括以下任意一种或几种的混合：丁酮肟、丁脒肟、丙酮肟、甲乙酮肟、甲醛肟、溴酚肟、环己酮肟、正庚醛肟、二甲基乙二肟、四甲基环丁二酮单肟。
在本发明的一种实施方式中，所述中和剂包括三乙胺、氨水、氢氧化钠、盐酸、醋酸、N,N-二甲基乙醇胺、二乙醇胺、三乙醇胺的一种或几种混合。
在本发明的一种实施方式中，所示步骤(1)中聚氨酯预聚体的制备方法具体包括：
将聚合物多元醇(占单体总质量的79％～95％)、亲水性扩链剂(占单体总质量的4％～11％)、含碳碳双键的双羟基小分子扩链剂(占单体总质量的1％～10％)在80～90℃下真空干燥出水3～4小时。按照异氰酸根与羟基比值在1.1～1.7，取部分亲水性扩链剂(占亲水性扩链剂总量的30％～40％)、聚合物多元醇，加入二月桂酸二丁基锡(占参与反应总单体质量的0.08％)，在氮气保护、温度70～80℃下滴加二异氰酸酯，采用二正丁胺法当测定反应体系内-NCO％值达到理论值后进行下一步(异氰酸根理论剩余量≤32～36％)。
本发明的一种实施方式中，所述步骤(2)具体包括：
在温度60～65℃下加入含碳碳双键的小分子扩链剂(式Ⅱ)，采用二正丁胺法测定反应体系内-NCO％含量达到理论值后进行下一步(异氰酸根理论剩余量≤12～16％)。再加入剩余亲 水性扩链剂直到反应体系内-NCO含量达到理论值(异氰酸根理论剩余量≤8％)。
在本发明的一种实施方式中，所述步骤(3)具体包括：
降低温度至50～60℃，按照加入封端剂对扩链后的聚氨酯封端(封端剂与未反应异氰酸根摩尔比值在1.5～2)，测定NCO％≤0.5％，完成聚氨酯封端。
在本发明的一种实施方式中，所述步骤(4)、(5)具体包括：
降低温度至室温，加入中和剂(中和度80％～100％)调节反应pH(pH＝7.5±0.5)，按照固含量20％～40％加入去离子水并高速搅拌(r＝1000～1600r/min)自乳化获得水性聚氨酯自乳液。
在本发明的一种实施方式中，所述步骤(6)具体包括：
在温度40～50℃下，将酯基碳原子数为1-18的丙烯酸酯单体缓慢加入到水性聚氨酯乳液内(丙烯酸酯单体总质量与侧链含碳碳双键的聚氨酯固含量比值在(1～4):1，在高速搅拌机下搅拌15～20min(r＝4000～5000r/min)，然后静置1～1.5h后升高温度至75～80℃，在3～4小时内缓慢滴加引发剂(占丙烯酸酯单体总质量的0.6～0.8％)，保温2～3h后降温出料，得到聚氨酯-丙烯酸酯类拒水剂(WPUA)。
本发明的第三个目的是制备一种疏水织物，所述织物包含上述聚氨酯-丙烯酸酯类拒水剂。
在本发明的一种实施方式中，所述疏水织物的制备工艺包括：采用轧-烘-焙工艺，织物以轧余率70-150％，浸轧浓度为20-180g/L，拒水剂乳液后在60-100℃预烘1-5min，在120-160℃焙烘1-5min。
本发明有益效果：
1、本发明通过含碳碳双键的双羟基小分子扩链剂(式Ⅱ)，将碳碳双键引入聚氨酯大分子侧链，利用聚氨酯侧链上的活性双键与丙烯酸酯类单体发生自由基聚合，制备聚氨酯-丙烯酸酯类拒水剂。在引入更多活性双键的同时获得较大分子量聚氨酯，使得参与接枝反应的丙烯酸酯单体增加，覆盖在聚氨酯分子链侧端，避免了因大分子链聚氨酯相互缠绕导致聚氨酯分子主链上的碳碳双键活性降低，增大了疏水基团在分子链中的含量，产生支化结构，提高了聚氨酯/丙烯酸酯相容性，获得性能稳定的拒水剂。
2、本发明采用无毒、低VOC含量、对环境友好的水性聚氨酯作为乳化剂与丙烯酸酯单体制备拒水剂，在聚氨酯末端采用肟类有机化合物对聚氨酯的异氰酸根封端，其在一定温度下发生解封闭发应，使得裸露在外端的异氰酸根与织物上的活泼氢基团发应，在拒水剂与织物之间通过化学键相互交联，解决了含氟类拒水剂环境污染问题以及长碳链拒水剂耐水洗牢度差的问题，使得织物的接触角高达152°以上、25次家庭洗衣机水洗的织物静态水接触角均高于140°。
附图说明
图1：经处理的织物的静态水接触角图。
具体实施方式
下面结合具体实例对本发明作进一步地说明，所举实例只用于解释本发明，并非用于限定本发明的范围。
实施例1
考察不同异氰酸根与羟基摩尔比值对拒水剂的影响：
按以下步骤制备一种聚氨酯-丙烯酸酯类拒水剂并整理织物：
聚氨酯-丙烯酸酯类拒水剂的制备：
侧链含碳碳双键的水性聚氨酯自乳液的制备：
(1)聚四氢呋喃(Mn＝850、占羟基总质量的95％)、2,2-二羟甲基丁酸(占羟基总质量的4％)、1,5-己二烯-3,4-二醇(占羟基总质量的1％)70℃下真空干燥除水3-4h后。在氮气保护和催化剂二月桂酸二丁基锡(占参与反应总单体质量的0.08％)存在下，将异氟尔酮二异氰酸酯缓慢滴加到含有聚四氢呋喃和30％的2,2-二羟甲基丁酸(异氰酸根与羟基摩尔比值分别为1.1、1.2、1.3、1.4、1.5、1.6、1.7)，反应温度80℃，采用二正丁胺法测定反应体系内-NCO含量达到理论值后进行下一步(异氰酸根理论剩余量≤32％)。
(2)降低温度至60℃，缓慢滴加三羟甲基丙烷单烯丙基醚(占羟基总质量的1％)，测定-NCO％值达到理论值后(异氰酸根理论剩余量≤12～16％)加入2,2-二羟甲基丁酸(占羟基总质量的4％)保温反应，直到反应体系内-NCO含量达到理论值(异氰酸根理论剩余量≤8％)；
(3)降低温度至50℃，丁酮肟对聚氨酯封端(反应体系内剩余异氰酸根含量与加入封端剂羟基摩尔比值为1.5)，测定NCO％≤0.5％后进行下一步；
(4)降低温度至室温，加入三乙胺(中和度80％)调节反应pH(pH＝7.5±0.5)，按照固含量20％加入去离子水并高速搅拌(r＝1000r/min)自乳化获得水性聚氨酯自乳液。
丙烯酸酯与侧链含碳碳双键水性聚氨酯自乳液反应制备拒水剂：
取上述侧链含碳碳双键的水性聚氨酯乳液升温至50℃，按照丙烯酸十二酯：丙烯酸丁酯：甲基丙烯酸甲酯摩尔比＝1:1:1，(丙烯酸酯单体与侧链含碳碳双键聚氨酯自乳液中含固量的质量比为1:1)逐滴加入到聚氨酯乳液内，在高速搅拌机下搅拌15min(r＝4000r/min)，然后静置1h后升高温度至75℃，在3小时内缓慢滴加过硫酸钾引发剂(占丙烯酸酯单体总质量的0.6％)，保温3h后降温出料，得到聚氨酯-丙烯酸酯类拒水剂(WPUA)。
聚氨酯-丙烯酸酯类拒水剂处理织物：
采用轧-烘-焙工艺，织物以轧余率70％，浸轧浓度为180g/L，拒水剂乳液后在100℃预烘3min，在140℃焙烘3min。处理后织物相关参数见表1。
表1不同异氰酸根与羟基摩尔比值制备的拒水剂性能
Figure PCTCN2019077205-appb-000003
注：耐水洗测试根据AATCC Test Method 61-2010《耐洗色牢度》中的2A测试标准进行，一次AATCC 2A标准的皂洗相当于5次普通家庭洗衣机的洗涤；在异氰酸根与羟基比值在1.1时，预聚体不易乳化，得到以异氰酸根封端的聚氨酯预聚体；在比值为1.7时，聚氨酯预聚体分子量过大，体系内残留-NCO含量增多，加水乳化是生成较多拒水性强脲基，乳液粒径过大，储存稳定性变差。
产品疏水效果：对比在不同比值下制备的聚氨酯丙烯酸酯拒水剂，当比值为1.1或1.7时，制备出的聚氨酯乳液不稳定，无法有效与丙烯酸酯类单体发生自由基聚合。比值在1.2-1.6时，拒水剂稳定，拒水效果较好，具备良好的抗起毛起球性能。
产品耐水洗牢度：在比值为1.2-1.6时制备的拒水剂乳液整理织物后，经过相当于25次家庭洗衣机水洗的织物静态水接触角(疏水性)均高于140°，具备较高的疏水性，说明利用本发明制备的拒水剂整理的织物具有较高的耐水洗牢度。
产品疏水效果重复性；利用异氰酸根与羟基摩尔比值为1.2-1.6时整理织物，经10次分批次整理，每次整理织物的静态水接触角的范围误差为±1°，由接触角数据可知，织物疏水效果重复性好。
实施例2
考察丙烯酸酯与水性聚氨酯自乳液的反应条件对拒水剂的影响：
聚氨酯自乳液的制备：选择异氰酸根与羟基摩尔比值为1.3，其他条件参照实施例1，制备得到聚氨酯自乳液。
丙烯酸酯与侧链含碳碳双键水性聚氨酯自乳液反应制备拒水剂：
取上述侧链含碳碳双键的水性聚氨酯乳液升温至50℃，将丙烯酸十二酯：丙烯酸丁酯：甲基丙烯酸甲酯摩尔比分别替换为2:1:0，1:2:0，0:2:1，0:1:2(丙烯酸酯单体与侧链含碳碳双键聚氨酯自乳液中含固量的质量比为1:1)逐滴加入到聚氨酯乳液内，在高速搅拌机下搅拌15min(r＝4000r/min)，然后静置1h后升高温度至75℃，在3小时内缓慢滴加过硫酸钾引发剂(占丙烯酸酯单体总质量的0.6％)，保温3h后降温出料，得到聚氨酯-丙烯酸酯类拒水剂(WPUA)。
聚氨酯-丙烯酸酯类拒水剂处理织物：
采用轧-烘-焙工艺，织物以轧余率70％，浸轧浓度为180g/L，拒水剂乳液后在100℃预烘3min，在140℃焙烘3min。处理后织物相关参数见表2。
表2不同丙烯酸酯单体反应制备的拒水剂性能
Figure PCTCN2019077205-appb-000004
注：耐水洗测试根据AATCC Test Method 61-2010《耐洗色牢度》中的2A测试标准进行.一次AATCC 2A标准的皂洗相当于5次普通家庭洗衣机的洗涤。
产品疏水效果：对比在不同丙烯酸酯单体比值下制备的聚氨酯丙烯酸酯拒水剂，拒水剂稳定，整理织物拒水效果较好，具备良好的抗起毛起球性能。
产品耐水洗牢度：对比在不同丙烯酸酯单体比值下制备的聚氨酯丙烯酸酯拒水剂，经过相当于25次家庭洗衣机水洗的织物静态水接触角(疏水性)均高于142°，具备较高的疏水性，说明利用本发明制备的拒水剂整理的织物具有较高的耐水洗牢度。
产品疏水效果重复性；对比在不同丙烯酸酯单体比值下制备的聚氨酯丙烯酸酯拒水剂，经10次分批次整理，每次整理织物的静态水接触角的范围误差为±1°，由接触角数据可知，织物疏水效果重复性好。
实施例3
按以下步骤制备一种聚氨酯-丙烯酸酯类拒水剂并整理织物：
聚氨酯-丙烯酸酯类拒水剂的制备：
侧链含碳碳双键的水性聚氨酯自乳液的制备：
(1)聚丙二醇(Mn＝2000、占羟基总质量的79％)、2,2-二羟甲基丙酸(占羟基总质量的11％)、7-辛烯-1,2-二醇(占羟基总质量的10％)70℃下真空干燥除水3-4h后。在氮气保护和催化剂二月桂酸二丁基锡(占参与反应总单体质量的0.08％)存在下，将对苯二异氰酸酯缓慢滴加到含有聚丙二醇和30％的2,2-二羟甲基丙酸(异氰酸根与羟基摩尔比值为1.3)，反应温度80℃，采用二正丁胺法测定反应体系内-NCO含量达到理论值后进行下一步(异氰酸根理论剩余量≤32％)。
(2)降低温度至65℃，缓慢滴加7-辛烯-1,2-二醇(占羟基总质量的10％)，测定-NCO％值达到理论值后(异氰酸根理论剩余量≤12％)加入2,2-二羟甲基丁酸(占羟基总质量的11％)保温反应，直到反应体系内-NCO含量达到理论值(异氰酸根理论剩余量≤8％)；
(3)降低温度至60℃，正庚醛肟对聚氨酯封端(反应体系内剩余异氰酸根含量与加入封端剂羟基摩尔比值为2)，测定NCO％≤0.5％后进行下一步；
(4)降低温度至室温，加入三乙胺(中和度100％)调节反应pH(pH＝7.5±0.5)，按照固含量40％加入去离子水并高速搅拌(r＝1600r/min)自乳化获得水性聚氨酯自乳液。
丙烯酸酯与侧链含碳碳双键水性聚氨酯自乳液反应制备拒水剂：
取上述侧链含碳碳双键的水性聚氨酯乳液升温至40℃，按照丙烯酸十八酯：丙烯酸十四酯：甲基丙烯酸甲酯＝2:1，(丙烯酸酯单体与侧链含碳碳双键聚氨酯自乳液中含固量的质量比为4:1)逐滴加入到聚氨酯乳液内，在高速搅拌机下搅拌20min(r＝5000r/min)，然后静置1.5h后升高温度至80℃，在4小时内缓慢滴加过硫酸钾引发剂(占丙烯酸酯单体总质量的0.8％)，保温2h后降温出料，得到聚氨酯-丙烯酸酯类拒水剂(WPUA)。
聚氨酯-丙烯酸酯类拒水剂处理织物：
采用轧-烘-焙工艺，织物以轧余率150％，浸轧浓度为20g/L，拒水剂乳液后在60℃预烘 5min，在160℃焙烘1min。处理后织物相关参数见表3。
实施例4
按以下步骤制备一种聚氨酯-丙烯酸酯类拒水剂并整理织物：
聚氨酯-丙烯酸酯类拒水剂的制备：
侧链含碳碳双键的水性聚氨酯自乳液的制备：
(1)聚-ε-己内酯二醇(Mn＝300、占羟基总质量的80％)、2,2-二羟甲基丁酸(占羟基总质量的10％)、6-庚烯-2,4-二醇(占羟基总质量的10％)70℃下真空干燥除水3-4h。在氮气保护和催化剂二月桂酸二丁基锡(占参与反应总单体质量的0.08％)存在下，将二苯基甲烷二异氰酸酯缓慢滴加到含有聚-ε-己内酯二醇和30％的二羟甲基丙酸(异氰酸根与羟基摩尔比值为1.3)，反应温度75℃，采用二正丁胺法测定反应体系内-NCO含量达到理论值后进行下一步(异氰酸根理论剩余量≤32％)；
(2)降低温度至60℃，缓慢滴加6-庚烯-2,4-二醇(占羟基总质量的10％)，测定-NCO％值达到理论值后(异氰酸根理论剩余量≤14％)加入2,2-二羟甲基丁酸(占羟基总质量的10％)保温反应，直到反应体系内-NCO含量达到理论值(异氰酸根理论剩余量≤8％)；
(3)降低温度至50℃，环己酮肟对聚氨酯封端(反应体系内剩余异氰酸根含量与加入封端剂羟基摩尔比值为1.8)，测定NCO％≤0.5％后进行下一步；
(4)降低温度至室温，加入三乙胺(中和度90％)调节反应pH(pH＝7.5±0.5)，按照固含量30％加入去离子水并高速搅拌(r＝1600r/min)自乳化获得水性聚氨酯自乳液。
丙烯酸酯与侧链含碳碳双键水性聚氨酯自乳液反应制备拒水剂：
取上述侧链含碳碳双键的水性聚氨酯乳液升温至50℃，按照甲基丙烯酸十二酯：丙烯酸丁酯＝1:2，(丙烯酸酯单体与侧链含碳碳双键聚氨酯自乳液中含固量的质量比为3:1)逐滴加入到聚氨酯乳液内，在高速搅拌机下搅拌15min(r＝4500r/min)，然后静置1h后升高温度至75℃，在3.5小时内缓慢滴加偶氮二异丁腈引发剂(占丙烯酸酯单体总质量的0.7％)，保温3h后降温出料，得到聚氨酯-丙烯酸酯类拒水剂(WPUA)。
聚氨酯-丙烯酸酯类拒水剂处理织物：
采用轧-烘-焙工艺，织物以轧余率100％，浸轧浓度为120g/L，拒水剂乳液后在90℃预烘3min，在140℃焙烘2min。处理后织物相关参数见表3。
实施例5
按以下步骤制备一种聚氨酯-丙烯酸酯类拒水剂并整理织物：
聚氨酯-丙烯酸酯类拒水剂的制备：
侧链含碳碳双键的水性聚氨酯自乳液的制备：
(1)聚己二酸乙二醇酯二醇(Mn＝1500、占羟基总质量的85％)、N-甲基二乙醇胺(占羟基总质量的10％)、季戊四醇二丙烯酸酯(占羟基总质量的5％)70℃下真空干燥除水3-4h。在氮气保护和催化剂二月桂酸二丁基锡(占参与反应总单体质量的0.08％)存在下，将4,4-二苯基甲烷二异氰酸酯缓慢滴加到含有聚己二酸乙二醇酯二醇和30％的N-甲基二乙醇胺(异氰酸根与羟基摩尔比值为1.3)，反应温度80℃，采用二正丁胺法测定反应体系内-NCO含量达到理论值后进行下一步(异氰酸根理论剩余量≤32％)。
(2)降低温度至50℃，缓慢滴加季戊四醇二丙烯酸酯(占羟基总质量的5％)，测定-NCO％值达到理论值后(异氰酸根理论剩余量≤14％)加入N-甲基二乙醇胺(占羟基总质量的10％)保温反应，直到反应体系内-NCO含量达到理论值(异氰酸根理论剩余量≤8％)；
(3)降低温度至60℃，丁酮肟对聚氨酯封端(反应体系内剩余异氰酸根含量与加入封端剂羟基摩尔比值为1.6)，测定NCO％≤0.5％后进行下一步；
(4)降低温度至室温，加入盐酸(中和度85％)调节反应pH(pH＝7.5±0.5)，按照固含量35％加入去离子水并高速搅拌(r＝1600r/min)自乳化获得水性聚氨酯自乳液。
丙烯酸酯与侧链含碳碳双键水性聚氨酯自乳液反应制备拒水剂：
取上述侧链含碳碳双键的水性聚氨酯乳液升温至45℃，按照丙烯酸十八酯：丙烯酸丁酯＝2:1，(丙烯酸酯单体与侧链含碳碳双键聚氨酯自乳液中含固量的质量比为2:1)逐滴加入到聚氨酯乳液内，在高速搅拌机下搅拌20min(r＝5000r/min)，然后静置1.5h后升高温度至80℃，在4小时内缓慢滴加偶氮二异丁腈引发剂(占丙烯酸酯单体总质量的0.6％)，保温2h后降温出料，得到聚氨酯-丙烯酸酯类拒水剂(WPUA)。
聚氨酯-丙烯酸酯类拒水剂处理织物：
采用轧-烘-焙工艺，织物以轧余率80％，浸轧浓度为160g/L，拒水剂乳液后在70℃预烘5min，在150℃焙烘4min。处理后织物相关参数见表3。
实施例6
按以下步骤制备一种聚氨酯-丙烯酸酯类拒水剂并整理织物：
聚氨酯-丙烯酸酯类拒水剂的制备：
侧链含碳碳双键的水性聚氨酯自乳液的制备：
(1)聚乙二醇(Mn＝600、占羟基总质量的90％)、二乙烯三胺(占羟基总质量的4％)、甲基丙烯酸甘油酯(占羟基总质量的6％)70℃下真空干燥除水3-4h。在氮气保护和催化剂二月桂酸二丁基锡(占参与反应总单体质量的0.08％)存在下，将间苯二异氰酸酯缓慢滴加到含有聚乙二醇和30％的二乙烯三胺(异氰酸根与羟基摩尔比值为1.3)，反应温度70℃，采用二正丁胺法测定反应体系内-NCO含量达到理论值后进行下一步(异氰酸根理论剩余量≤32％)。
(2)降低温度至60℃，缓慢滴加甲基丙烯酸甘油酯(占羟基总质量的6％)，测定-NCO％值达到理论值后(异氰酸根理论剩余量≤14％)加入二乙烯三胺(占羟基总质量的4％)保温反应，直到反应体系内-NCO含量达到理论值(异氰酸根理论剩余量≤8％)；
(3)降低温度至50℃，二甲基乙二肟对聚氨酯封端(反应体系内剩余异氰酸根含量与加入封端剂羟基摩尔比值为1.5)，测定NCO％≤0.5％后进行下一步；
(4)降低温度至室温，加入盐酸(中和度95％)调节反应pH(pH＝7.5±0.5)，按照固含量25％加入去离子水并高速搅拌(r＝1600r/min)自乳化获得水性聚氨酯自乳液。
丙烯酸酯与侧链含碳碳双键水性聚氨酯自乳液反应制备拒水剂：
取上述侧链含碳碳双键的水性聚氨酯乳液升温至40℃，按照丙烯酸己酯：甲基丙烯酸己酯:甲基丙烯酸辛酯＝1:1:1，(丙烯酸酯单体与侧链含碳碳双键聚氨酯自乳液中含固量的质量比为3:1)逐滴加入到聚氨酯乳液内，在高速搅拌机下搅拌15min(r＝5000r/min)，然后静置1h后升高温度至75℃，在4小时内缓慢滴加过硫酸钾引发剂(占丙烯酸酯单体总质量的0.7％)，保温3h后降温出料，得到聚氨酯-丙烯酸酯类拒水剂(WPUA)。
聚氨酯-丙烯酸酯类拒水剂处理织物：
采用轧-烘-焙工艺，织物以轧余率70％，浸轧浓度为180g/L，拒水剂乳液后在60℃预烘5min，在150℃焙烘2min。处理后织物相关参数见表3。
对照例1
按以下步骤制备嵌段式水性聚氨酯改性丙烯酸酯类拒水剂并整理织物：
末端含碳碳双键水性聚氨酯自乳液的制备：
(1)聚四氢呋喃(Mn＝850、占羟基总质量的95％)、2,2-二羟甲基丁酸(占羟基总质量的4％)、丙烯酸羟乙酯(占羟基总质量的1％)70℃下真空干燥除水2-3h后。在氮气保护和催化剂二月桂酸二丁基锡(占参与反应总单体质量的0.08％)存在下，将异氟尔酮二异氰酸酯缓慢滴加到含有聚四氢呋喃和30％的2,2-二羟甲基丁酸(异氰酸根与羟基摩尔比值为1.3)，反应温度80℃，采用二正丁胺法测定反应体系内-NCO含量达到理论值后进行下一步(异氰酸根理论剩余量≤32％)。
(2)降低温度至60℃，缓慢滴加入2,2-二羟甲基丁酸(占羟基总质量的4％)保温反应，直到反应体系内-NCO含量达到理论值(异氰酸根理论剩余量≤8％)；
(3)降低温度至50℃，加入丙烯酸羟乙酯对聚氨酯封端(反应体系内剩余异氰酸根含量与加入封端剂羟基摩尔比值为1.5)，测定NCO％≤0.5％后进行下一步；
(4)降低温度至室温，加入三乙胺(中和度80％)调节反应pH(pH＝7.5±0.5)，按照固含量20％加入去离子水并高速搅拌(r＝1000r/min)自乳化获得水性聚氨酯自乳液。
丙烯酸酯与侧链含碳碳双键水性聚氨酯自乳液反应制备拒水剂：
取上述侧链含碳碳双键的水性聚氨酯乳液升温至50℃，按照丙烯酸十二酯：丙烯酸丁酯：甲基丙烯酸甲酯＝1:1:1，(丙烯酸酯单体与侧链含碳碳双键聚氨酯自乳液中含固量的质量比为1:1)逐滴加入到聚氨酯乳液内，在高速搅拌机下搅拌15min(r＝4000r/min)，然后静置1h后升高温度至75℃，在3小时内缓慢滴加过硫酸钾引发剂(占丙烯酸酯单体总质量的0.6％)，保温3h后降温出料，得到聚氨酯-丙烯酸酯类拒水剂(WPUA)。
聚氨酯-丙烯酸酯类拒水剂处理织物：
采用轧-烘-焙工艺，织物以轧余率70％，浸轧浓度为180g/L，拒水剂乳液后在100℃预烘3min，在140℃焙烘3min。处理后织物相关参数见表3。
对照例2
按以下步骤制备接枝式水性聚氨酯改性丙烯酸酯类拒水剂并整理织物：
主链内部含碳碳双键水性聚氨酯自乳液的制备：
(1)聚四氢呋喃(Mn＝850、占羟基总质量的95％)、2,2-二羟甲基丁酸(占羟基总质量的4％)、丁烯二醇(占羟基总质量的1％)70℃下真空干燥除水2-3h后。在氮气保护和催化剂二月桂酸二丁基锡(占参与反应总单体质量的0.08％)存在下，将异氟尔酮二异氰酸酯缓慢滴加到含有聚四氢呋喃和30％的2,2-二羟甲基丁酸(异氰酸根与羟基摩尔比值为1.3)，反应温度80℃，采用二正丁胺法测定反应体系内-NCO含量达到理论值后进行下一步(异氰酸根理论剩余量≤32％)。
(2)降低温度至60℃，缓慢滴加丁烯二醇(占羟基总质量的1％)，测定-NCO％值达到理论值后(异氰酸根理论剩余量≤14％)加入2,2-二羟甲基丁酸占羟基总质量的4％)保温反应，直到反应体系内-NCO含量达到理论值(异氰酸根理论剩余量≤8％)；
(3)降低温度至50℃，加入丁酮肟对聚氨酯封端(反应体系内剩余异氰酸根含量与加入封端剂羟基摩尔比值为1.5)，测定NCO％≤0.5％后进行下一步；
(4)降低温度至室温，加入三乙胺(中和度80％)调节反应pH(pH＝7.5±0.5)，按照固含量20％加入去离子水并高速搅拌(r＝1000r/min)自乳化获得水性聚氨酯自乳液。
丙烯酸酯与主链含碳碳双键水性聚氨酯自乳液反应制备拒水剂：
取上述侧链含碳碳双键的水性聚氨酯乳液升温至50℃，按照丙烯酸十二酯：丙烯酸丁酯：甲基丙烯酸甲酯＝1:1:1，(丙烯酸酯单体与侧链含碳碳双键聚氨酯自乳液中含固量的质量比为1:1)逐滴加入到聚氨酯乳液内，在高速搅拌机下搅拌15min(r＝4000r/min)，然后静置1h后升高温度至75℃，在3小时内缓慢滴加过硫酸钾引发剂(占丙烯酸酯单体总质量的0.6％)，保温3h后降温出料，得到聚氨酯-丙烯酸酯类拒水剂(WPUA)。
聚氨酯-丙烯酸酯类拒水剂处理织物：
采用轧-烘-焙工艺，织物以轧余率70％，浸轧浓度为180g/L，拒水剂乳液后在100℃预烘3min，在140℃焙烘3min。处理后织物相关参数见表3。
对照例3
参照实施例6，其他条件不变，将含双羟基的双键单体替换为1,5-己二烯-3,4-二醇，制备得到疏水织物。相关测试结果见表3。
表3不同拒水剂处理后的织物相关参数
Figure PCTCN2019077205-appb-000005
注：耐水洗测试根据AATCC Test Method 61-2010《耐洗色牢度》中的2A测试标准进行.一次AATCC 2A标准的皂洗相当于5次普通家庭洗衣机的洗涤。
产品疏水效果：本发明利用含双碳碳双键的双羟基小分子扩链剂在聚氨酯侧链引入碳碳双键(实施例1-6)，与在聚氨酯末端引入碳碳双键(对照例1)以及在聚氨酯主链内部引入碳碳双键(对照例2、对照例3)相比，按照实施例1-6步骤所制备拒水剂较稳定，整理织物拒水效果较好，具备良好的抗起毛起球性能。
产品耐水洗牢度：对比实施例1-6在不同丙烯酸酯单体比值下制备的聚氨酯丙烯酸酯拒水剂，经过相当于25次家庭洗衣机水洗的织物静态水接触角(疏水性)均高于142°，具备较高的疏水性，说明利用本发明制备的拒水剂整理的织物具有较高的耐水洗牢度。
产品疏水效果重复性；对比实施例1-6在不同丙烯酸酯单体比值下制备的聚氨酯丙烯酸酯拒水剂，经10次分批次整理，每次整理织物的静态水接触角的范围误差为±1°，由接触角 数据可知，织物疏水效果重复性好。
以上所述，仅是本发明的优选实施方式，应当指出，对于本技术领域的普通技术人员来说，在不脱离本发明原理的前提下，还可以做出若干改进和润饰，这些改进和润饰也应视为本发明的保护范围。

Claims (17)

  1. 一种聚氨酯-丙烯酸酯类拒水剂，其特征在于，所述拒水剂是在聚氨酯侧链引入碳碳双键，其结构式如式(I)所示：
    Figure PCTCN2019077205-appb-100001
    其中，R 1为肟类封端；R 2为二异氰酸酯单体；R 3选自任意碳原子数的烷基、苯基、环基、酰基、酯基、羰基、醚基；R 4选自烷基、环基及其衍生物、苯基及其衍生物；R 5为碳原子个数1-18的碳链；R 6为聚醚或聚醇多元有机化物；R 7为亲水性扩链剂；a，n为1-100的自然数；
    所述拒水剂是利用如下方法制备得到的：
    (1)利用二异氰酸酯、部分亲水性扩链剂和聚合物多元醇制备聚氨酯预聚体；
    (2)聚氨酯预聚体与含双碳碳双键的双羟基小分子扩链剂、剩余亲水性扩链剂继续反应一段时间得到侧链含有碳碳双键的水性聚氨酯乳液；所述含双碳碳双键的双羟基小分子扩链剂包括以下任意一种或多种的混合：7-辛烯-1,2-二醇、季戊四醇二丙烯酸酯、6-庚烯-2,4-二醇、3-烯丙氧基-1,2-丙二醇、甲基丙烯酸甘油酯、三羟甲基丙烷单烯丙基醚、2,2-双羟基甲基丁酸-3-羟基-2-(2-甲基丙烯酰氧基)-丙酯、2-(3-异氰酸根合甲基)-3,5,5-三甲基环己基氨基甲酰基氧)丙烯酸乙酯；
    (3)加入肟类封端剂，对异氰酸根封端(NCO％≤0.5％)；
    (4)降温，加入中和剂调节pH＝7～8.5；
    (5)加入去离子水进行乳化得到侧链含碳碳双键的水性聚氨酯乳液；
    (6)将侧链含碳碳双键的聚氨酯乳液与丙烯酸酯类单体在引发剂条件下自由基聚合，得到聚氨酯-丙烯酸酯类拒水剂。
  2. 一种聚氨酯-丙烯酸酯类拒水剂，其特征在于，所述拒水剂是在聚氨酯侧链引入碳碳双键，其结构式如式(I)所示：
    Figure PCTCN2019077205-appb-100002
    Figure PCTCN2019077205-appb-100003
    其中，R 1为肟类封端剂；R 2为二异氰酸酯单体；R 3选自任意碳原子数的烷基、苯基、环基、酰基、酯基、羰基、醚基；R 4选自烷基、环基及其衍生物、苯基及其衍生物；R 5为碳原子个数1-18的碳链；R 6为聚醚或聚醇多元有机化物；R 7为亲水性扩链剂；a，n为1-100的自然数。
  3. 一种权利要求2所述的聚氨酯-丙烯酸酯类拒水剂的制备方法，其特征在于，所述方法包括：
    (1)利用二异氰酸酯、部分亲水性扩链剂和聚合物多元醇制备聚氨酯预聚体；
    (2)聚氨酯预聚体与含双碳碳双键的双羟基小分子扩链剂、剩余亲水性扩链剂继续反应一段时间得到侧链含有碳碳双键的水性聚氨酯乳液；所述含双碳碳双键的双羟基小分子扩链剂为式(II)所示化合物；
    (3)加入肟类封端剂，对异氰酸根封端(NCO％≤0.5％)；
    (4)降温，加入中和剂调节pH＝7～8.5；
    (5)加入去离子水进行乳化得到侧链含碳碳双键的水性聚氨酯乳液；
    (6)将侧链含碳碳双键的聚氨酯乳液与丙烯酸酯类单体在引发剂条件下自由基聚合，得到聚氨酯-丙烯酸酯类拒水剂；
    Figure PCTCN2019077205-appb-100004
    其中，R 3选自任意碳原子数的烷基、苯基、环基、酰基、酯基、羰基、醚基；R 4选自烷基、环基及其衍生物、苯基及其衍生物。
  4. 根据权利要求3所述的方法，其特征在于，所述含碳碳双键的双羟基小分子扩链剂包括以下任意一种或多种的混合：7-辛烯-1,2-二醇、季戊四醇二丙烯酸酯、6-庚烯-2,4-二醇、3-烯丙氧基-1,2-丙二醇、甲基丙烯酸甘油酯、三羟甲基丙烷单烯丙基醚、2,2-双羟基甲基丁酸-3-羟基-2-(2-甲基丙烯酰氧基)-丙酯、2-(3-异氰酸根合甲基)-3,5,5-三甲基环己基氨基甲酰基氧)丙烯酸乙酯。
  5. 根据权利要求3所述的方法，其特征在于，所述步骤(1)中聚氨酯预聚体的异氰酸根与羟基的摩尔比值为1.1～1.7。
  6. 根据权利要求4所述的方法，其特征在于，所述步骤(1)中聚氨酯预聚体的异氰酸根与羟基的摩尔比值为1.1～1.7。
  7. 根据权利要求3所述的方法，其特征在于，所述步骤(1)中亲水性扩链剂占单体总质量的4％～11％。
  8. 根据权利要求4所述的方法，其特征在于，所述步骤(2)中的含碳碳双键的双羟基小分子扩链剂占单体总质量的1％～10％。
  9. 根据权利要求3所述的方法，其特征在于，所述步骤(5)加水自乳化按照固含量20％～40％搅拌而得。
  10. 根据权利要求4所述的方法，其特征在于，所述步骤(5)加水自乳化按照固含量20％～40％搅拌而得。
  11. 根据权利要求5所述的方法，其特征在于，所述步骤(5)加水自乳化按照固含量20％～40％搅拌而得。
  12. 根据权利要求6所述的方法，其特征在于，所述步骤(5)加水自乳化按照固含量20％～40％搅拌而得。
  13. 根据权利要求7所述的方法，其特征在于，所述步骤(5)加水自乳化按照固含量20％～40％搅拌而得。
  14. 根据权利要求8所述的方法，其特征在于，所述步骤(5)加水自乳化按照固含量20％～40％搅拌而得。
  15. 根据权利要求3-14任一所述的方法，其特征在于，所述步骤(6)中丙烯酸酯单体与侧链含碳碳双键的聚氨酯自乳液中含固量的质量比为(1～4):1。
  16. 权利要求2所述的拒水剂在疏水技术领域中的应用。
  17. 一种疏水织物，其特征在于，将织物浸渍于含有权利要求2所述的拒水剂的处理液中进行处理后，轧烘焙后即得疏水织物。
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