Network structure stiffening agent copolymer and preparation method thereof

Abstract

The invention discloses a network structure stiffening agent copolymer and a preparation method thereof. The copolymer comprises the following copolymerization units: 1) 40-80 wt% of a copolymerization unit represented by a formula I; 2) 19 to 50 wt% of a methacrylic acid C1-C8 alkyl ester copolymerization unit; and 3) 1-15 wt% of a (meth) acrylic acid copolymerization unit. And the cationic emulsifier and the nonionic emulsifier are compounded for use, so that the emulsion has good stability. The copolymer is of a net-shaped structure, has a good stiffening effect, can be used for stiffening finishing of various fabrics, and can also be matched with an organic silicon product to adjust the hand feeling of the fabrics. * in the formula represents the position of double-bond copolymerization. # imgabs0 #

Description

Technical Field

[0001] The invention relates to the field of textile auxiliaries, in particular to a network structure stiffening agent copolymer and a preparation method thereof. Background Art

[0002] Stiffener is a substance used for stiffening textiles. Stiffener can form a film or cross-link inside the fiber, between the fibers or on the fiber surface, so that the fabric has a stiff, thick and full feel. At present, the commonly used stiffeners in China include melamine resin, polyvinyl acetate and polyacrylate stiffeners.

[0003] Fabrics finished with melamine stiffeners will release formaldehyde for a long time and have poor safety in use. In addition, the finishing cross-linking temperature of this finishing agent is high, and the fabric is prone to yellowing and strength loss. Polyvinyl acetate stiffeners have poor cold resistance and are prone to demulsification and coagulation at low temperatures. The emulsion has poor toughness after film formation and curing. The finished fabric feels rough and has poor scratch resistance. Polyacrylate stiffeners have good water resistance, weather resistance and mechanical properties, good film-forming properties and strong adhesion, but they are sticky when hot and brittle when cold, and their use is subject to certain restrictions.

[0004] Usually, in order to make the fabric feel more in line with market demand, stiffeners and softeners need to be used in combination. However, polyvinyl acetate stiffeners are generally anionic products. When used in combination with silicone softeners, they will demulsify and produce small particles, causing fabric pollution and affecting production efficiency.

[0005] Therefore, developing an environmentally friendly, effective and highly applicable stiffening agent has broad market prospects and practical significance. Summary of the invention

[0006] One aspect of the present invention is to provide a network structure stiffener copolymer, comprising the following copolymerization units:

[0007] 1) 40-80% by weight of copolymer units represented by formula I;

[0008] 2) 19-50 wt% of C1-C8 alkyl methacrylate copolymer units;

[0009] 3) 1-15 wt% of (meth)acrylic acid copolymerized units.

[0010]

[0011] In the formula, * indicates the position of the double bond copolymerization.

[0012] Another aspect of the present invention is to provide a method for preparing the above-mentioned network structure stiffener copolymer, comprising the following steps:

[0013] 1) dissolving a cationic emulsifier and a nonionic emulsifier in water to prepare a solution;

[0014] 2) adding the solution obtained in step 1) to the premixed solution of the comonomers and shearing at high speed to prepare a pre-emulsion;

[0015] 3) heating the pre-emulsion obtained in step 2) to 60-80° C., adding an initiator for initiation, and keeping the temperature for 3-5 hours;

[0016] 4) Cool down to room temperature and collect the material.

[0017] Compared with the currently disclosed stiffeners and preparation methods thereof, the network structure stiffener copolymer of the present invention has the following advantages: 1) the copolymer unit shown in formula I has both a melamine-like structure and a benzene ring, which helps to improve the stiffness of the stiffener; 2) the copolymer unit shown in formula I contains two double bonds, which can form a network copolymer by copolymerization with the acrylate copolymer unit, and has large steric hindrance and high crosslinking density, which helps to improve the stiffening effect; 3) it is stable when used in combination with silicone softeners, will not demulsify and produce small particles, and helps to improve the hand feel. DETAILED DESCRIPTION

[0018] In a preferred embodiment, the network structure stiffener copolymer of the present invention comprises the following copolymerization units:

[0019] 1) 45-75% by weight of copolymer units represented by formula I;

[0020] 2) 23-45 wt% C1-C8 alkyl methacrylate copolymer units;

[0021] 3) 2-10 wt% (meth)acrylic acid copolymer units.

[0022]

[0023] In the formula, * indicates the position of the double bond copolymerization.

[0024] In a preferred embodiment, the copolymer unit represented by formula I is obtained by the reaction of melamine and 3-isopropyl-dimethylbenzyl isocyanate.

[0025] In a preferred embodiment, the C1-C8 alkyl methacrylate is preferably a C1-C4 alkyl methacrylate.

[0026] In a preferred embodiment, the preparation method of the super network structure stiffener copolymer of the present invention comprises the following steps:

[0027] 1) dissolving a cationic emulsifier and a nonionic emulsifier in water to prepare a solution;

[0028] 2) adding the solution obtained in step 1) to the premixed solution of the comonomers and shearing at high speed to prepare a pre-emulsion;

[0029] 3) heating the pre-emulsion obtained in step 2) to 60-80° C., adding an initiator for initiation, and keeping the temperature for 3-5 hours;

[0030] 4) Cool down to room temperature and collect the material.

[0031] In a preferred embodiment, the cationic emulsifier is selected from one or both of C12-C18 alkyl trimethyl ammonium chloride and C12-C18 alkyl trimethyl ammonium bromide.

[0032] In a preferred embodiment, the nonionic emulsifier is selected from one or both of isomeric C10-C13 alcohol polyoxyethylene ethers with an EO number of 5-20 and C8-C20 fatty alcohol polyoxyethylene ethers with an EO number of 15-40.

[0033] In a preferred embodiment, the free radical initiator is an azo initiator, such as azobisisobutyronitrile hydrochloride.

[0034] The network structure stiffener copolymer prepared by the present invention has a melamine-like structure and a benzene ring in its structure, which helps to improve the stiffness of the stiffener; and as shown in Formula I, the copolymer unit contains two double bonds, which can be copolymerized with the acrylate copolymer unit to form a network copolymer with large steric hindrance and high crosslinking density, which helps to improve the stiffening effect; when used in combination with an organosilicon softener, it is stable and will not break the emulsion to produce small particles, which helps to improve the hand feel.

[0035] Example

[0036] The present invention will be further described below in conjunction with specific embodiments. It should be understood that these embodiments are only used to illustrate the present invention and are not intended to limit the scope of the present invention. In addition, it should be understood that after reading the content taught by the present invention, those skilled in the art can make various changes or modifications to the present invention, and these equivalent forms fall within the scope limited by the appended claims of the application equally.

[0037] In each embodiment, all raw materials and fabrics are commercially available.

[0038] The high-speed shearing mentioned in the present invention is stirring using a conventional laboratory high-speed shearing mixer in the art.

[0039] The performance measurement and application effect in each embodiment are measured and evaluated according to the following methods:

[0040] 1. Stability

[0041] Storage stability: Store at room temperature and observe for stratification or precipitation after 6 months.

[0042] Application stability: Observe the liquid level status during application experiments.

[0043] Working solution stability: Place the prepared working solution at room temperature for 3 hours and observe whether stratification or precipitation occurs.

[0044] 2. Fabric treatment process:

[0045] 2.1 Fabric finishing with stiffening agent alone

[0046] The dosage of stiffening agent is 50g / L.

[0047] Process: one dip and one rolling at 150℃×2min.

[0048] 2.2 Use with silicone softener

[0049] The dosage of stiffening agent is 50g / L.

[0050] Silicone softener: Yakeshu KC-38H 20g / L

[0051] Process: one dip and one rolling at 150℃×2min.

[0052] 3. Test standards and methods for stiffness of the products produced

[0053] The stiffness test method is determined in accordance with “GB / T 18318-2001 Textiles - Determination of Bending Length of Textile Fabrics”.

[0054] 4. Hand feel test method

[0055] The feel of the original fabric was scored as 1 point, and the average value was taken based on the evaluation results of 5 people (1-5 points, 1 point is the worst and 5 points is the best).

[0056] Example 1

[0057] Dissolve 37.8g (0.3mol) of melamine in dimethyl sulfoxide in a dry and clean 500ml four-necked bottle, add 20.1g (0.1mol) of 3-isopropyl-dimethylbenzyl isocyanate and 3 drops of dibutyltin dilaurate under nitrogen protection, heat to 90℃, keep warm for 2h, adjust the viscosity of the system with acetone during the reaction, cool to 40-45℃ and neutralize with triethylamine, react for 1h, and cool to room temperature. Add 35g of ethyl methacrylate and 7.1g of acrylic acid.

[0058] Take another beaker, add 3g C16 fatty alcohol polyoxyethylene ether (15EO), 3g hexadecyltrimethylammonium bromide and 184g water, heat to 70°C to dissolve, then add to the four-necked bottle in the above step, high-speed shear for 1h, then heat to 72°C, add 10g 1% azobisisobutyronitrile hydrochloride to initiate, maintain 72°C, react for 4h, cool to room temperature, and obtain stiffening agent 1.

[0059] Example 2

[0060] Dissolve 37.8g (0.3mol) of melamine in dimethyl sulfoxide in a dry and clean 500ml four-necked bottle, add 20.1g (0.1mol) of 3-isopropyl-dimethylbenzyl isocyanate and 3 drops of dibutyltin dilaurate under nitrogen protection, heat to 90℃, keep warm for 2h, adjust the viscosity of the system with acetone during the reaction, cool to 40-45℃ and neutralize with triethylamine, react for 1h, cool to room temperature, add 22g of butyl methacrylate and 2g of methacrylic acid.

[0061] Take another beaker, add 2.5g C18 fatty alcohol polyoxyethylene ether (10EO), 2.5g octadecyltrimethylammonium chloride and 160.9g water, heat to 70°C to dissolve, then add to the four-necked bottle in the above step, high-speed shear for 1h, then heat to 74°C, add 8.2g 1% azobisisobutyronitrile hydrochloride to initiate, maintain 74°C, react for 3.5h, cool to room temperature, and obtain stiffening agent 2.

[0062] Example 3

[0063] Dissolve 37.8g (0.3mol) of melamine in dimethyl sulfoxide in a dry and clean 500ml four-necked bottle, add 20.1g (0.1mol) of 3-isopropyl-dimethylbenzyl isocyanate and 3 drops of dibutyltin dilaurate under nitrogen protection, heat to 90℃, keep warm for 2h, adjust the viscosity of the system with acetone during the reaction, cool to 40-45℃ and neutralize with triethylamine, react for 1h, and cool to room temperature. Add 50.6g of methyl methacrylate and 11.5g of acrylic acid.

[0064] Take another beaker, add 3.6g C13 isomeric alcohol polyoxyethylene ether (20EO), 3.6g dodecyltrimethylammonium chloride and 202.8g water, heat to 70°C to dissolve, then add to the four-necked bottle in the above step, high-speed shear for 1h, then heat to 70°C, add 12g 1% azobisisobutyronitrile hydrochloride to initiate, maintain 70°C, react for 4.5h, cool to room temperature, and obtain stiffening agent 3.

[0065] Table 1 Stability

[0066]

[0067] Table 2 Stiffness

[0068]

[0069] Table 3 Hand feel style and working fluid stability

[0070]

[0071] Note: Fabric is N / R Roman cloth

[0072] It can be seen from the data in Table 2 that, compared with the commercially available stiffeners, the stiffener prepared by the present invention has a good stiffening effect when used to finish different fabrics. After being placed for one month, the fabrics are basically not softened and still maintain good stiffness. Table 3 shows that the stiffener of the present invention is used in combination with the silicone softener, and has good stability, which can make the fabric have a firm and elastic feel.

[0073] Although the present invention has been disclosed as above by way of embodiments, it is not intended to limit the protection scope of the present invention. Any changes and modifications made by any technician familiar with the technology without departing from the concept and scope of the present invention should fall within the protection scope of the present invention.

Claims

1. A network structure stiffener copolymer comprising the following copolymerization units: 1) 40-80% by weight of copolymer units represented by formula I; 2) 19-50 wt% of C1-C8 alkyl methacrylate copolymer units; 3) 1-15 wt% (meth)acrylic acid copolymer units, In the formula, * indicates the position of the double bond copolymerization.

2. The network structure stiffener copolymer according to claim 1, comprising the following copolymerization units: 1) 45-75% by weight of copolymer units represented by formula I; 2) 23-45 wt% C1-C8 alkyl methacrylate copolymer units; 3) 2-10 wt% (meth)acrylic acid copolymer units, In the formula, * indicates the position of the double bond copolymerization.

3. The network structure stiffener copolymer according to claim 1 or 2, characterized in that: The copolymer unit shown in formula I is obtained by the reaction of melamine and 3-isopropyl-dimethylbenzyl isocyanate.

4. A method for preparing a network structure stiffener copolymer according to any one of claims 1 to 3, the method comprising the following steps: 1) dissolving a cationic emulsifier and a nonionic emulsifier in water to prepare a solution; 2) adding the solution obtained in step 1) to the premixed solution of the comonomers and shearing at high speed to prepare a pre-emulsion; 3) heating the pre-emulsion obtained in step 2) to 60-80° C., adding an initiator for initiation, and keeping the temperature for 3-5 hours; 4) Cool down to room temperature and collect the material.

5. The method for preparing a network structure stiffener copolymer as claimed in claim 4, wherein the cationic emulsifier is selected from one or both of C12-C18 alkyl trimethyl ammonium chloride and C12-C18 alkyl trimethyl ammonium bromide.

6. The method for preparing a network structure stiffener copolymer as claimed in claim 4, wherein the nonionic emulsifier is selected from one or both of isomeric C10-C13 alcohol polyoxyethylene ethers with an EO number of 5-20 and C8-C20 fatty alcohol polyoxyethylene ethers with an EO number of 15-40.

7. The method for preparing a network structure stiffener copolymer according to claim 4, characterized in that: The initiator is an azo initiator.

8. The method for preparing a network structure stiffener copolymer according to claim 7, characterized in that: The initiator is azobisisobutyronitrile hydrochloride.

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