CN110565377B - Organosilicon quaternary ammonium salt for improving whiteness and softness of fabric and preparation method and emulsion thereof - Google Patents
Organosilicon quaternary ammonium salt for improving whiteness and softness of fabric and preparation method and emulsion thereof Download PDFInfo
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- 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
- D06M13/00—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment
- D06M13/50—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment with organometallic compounds; with organic compounds containing boron, silicon, selenium or tellurium atoms
- D06M13/51—Compounds with at least one carbon-metal or carbon-boron, carbon-silicon, carbon-selenium, or carbon-tellurium bond
- D06M13/513—Compounds with at least one carbon-metal or carbon-boron, carbon-silicon, carbon-selenium, or carbon-tellurium bond with at least one carbon-silicon bond
- D06M13/5135—Unsaturated compounds containing silicon atoms
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- 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
- D06M16/00—Biochemical treatment of fibres, threads, yarns, fabrics, or fibrous goods made from such materials, e.g. enzymatic
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- 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
- D06M2200/50—Modified hand or grip properties; Softening compositions
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Abstract
The invention discloses an organosilicon quaternary ammonium salt for improving whiteness and softness of fabrics, which has the following structural formula:
Description
Technical Field
The invention relates to the field of fabric modifiers, in particular to an organosilicon quaternary ammonium salt for improving whiteness and softness of fabrics, a preparation method thereof and an emulsion.
Background
Silicones are widely used as fabric softeners, a class of chemicals that change the static and dynamic coefficients of friction of fibers. When the static friction coefficient is changed, the hand feeling is smooth and easy to move on the fiber or fabric; when the coefficient of dynamic friction is changed, the fine structures between the fibers tend to move relative to each other, that is, the fibers or the fabric tend to be deformed. The combined feel of the two is soft. The softening agent is classified into four types, i.e., a cationic type, a nonionic type, an anionic type, and an amphoteric quaternary ammonium salt type, in terms of ionic properties.
The present application mainly discusses a quaternary ammonium salt type softener, and D1821 (dioctadecyldimethylammonium chloride), which is a typical representative in the market, is a mature softener with antibacterial property. Through comprehensive tests, the yellowing resistance of the composite material can reach about 96%.
However, we are looking at a product that cannot be considered from the standpoint of its properties alone, and we focus on the properties of a softener in three main areas: anti-yellowing performance, antibacterial performance and softness performance.
The main object of the present application is to achieve a synergistic improvement in yellowing resistance and flexibility by introducing a combination of silicone and quaternary ammonium salt.
CN201410815486.4 discloses a hydrophilic softening agent for towel fabrics, belonging to the field of textile fabric softening agents. The softening agent comprises the following components in percentage by mass: 10 to 20 percent of modified amino siloxane, 5 to 10 percent of polyether polyester, 1 to 8 percent of quaternary ammonium salt, 5 to 10 percent of non-ionic emulsifier, 0.1 to 0.5 percent of organic acid and 51.5 to 78.9 percent of deionized water.
CN201410842073.5 discloses a softener for rayon embroidery threads, belonging to the field of fabric softeners. The components by mass percent are as follows: 10 to 30 percent of modified amino siloxane, 1 to 8 percent of quaternary ammonium salt, 5 to 15 percent of non-ionic emulsifier, 0.1 to 0.5 percent of organic acid and 46.5 to 83.9 percent of deionized water.
The two technologies are only mixed when being introduced, and the change of the molecular structure is not involved, so the anti-yellowing performance and the softness performance cannot be synergistically improved.
CN201710997002.6 discloses a super-hydrophilic low-yellowing organic silicon softening agent and a preparation method thereof, wherein polysiloxane containing alkoxy, ether and quaternary ammonium groups and an emulsifier are added into an emulsifying kettle, stirred for 5-30 min, then acetic acid is added to adjust the pH value to 5-6, finally glycerol and deionized water are added, and stirring is continued for 10-40 min, so that the super-hydrophilic low-yellowing organic silicon softening agent is prepared. The organic silicon softening agent prepared by the invention has good hydrophilicity, can achieve instant hydrophilicity (less than 1s), has low yellow degree and yellowing rate of less than 0.4 percent, has good stability, is washable and has a stiff and smooth hand feeling. The preparation method is simple and easy to implement, has lower requirements on production equipment, and is easy to realize industrial production.
Although the technical effects of this technique are described in the description of the hand, stiffness, smoothness and the like, the description of the properties of flexibility is not clear and sufficient compared with the commercially available product D1821.
It was therefore an object of the present application to develop a quaternary silicone salt which is superior in part of its properties to the commercial product D1821.
Disclosure of Invention
The invention aims to provide a quaternary ammonium silicone salt for improving whiteness and softness of fabrics, which has excellent properties of softness and yellowing resistance, and also provides a preparation method of the quaternary ammonium silicone salt and an emulsion containing the quaternary ammonium silicone salt.
In order to achieve the purpose, the invention provides the following technical scheme: a quaternary ammonium silicone salt for improving whiteness and softness of fabrics, wherein the quaternary ammonium silicone salt has the following structural formula:
wherein R is unsaturated fatty group of C15-C17 or unsaturated fatty group of C15-C17 substituted by fluorine.
In the above quaternary ammonium silicone salt for improving whiteness and softness of fabric, the structural formula of the quaternary ammonium silicone salt is as follows:
wherein n in the formulas 2 and 3 is 12-14.
In the quaternary ammonium salt of silicone for improving whiteness and softness of fabric, n is 13.
Meanwhile, the invention also discloses a preparation method of the organosilicon quaternary ammonium salt as claimed in claim 2 or 3, which comprises the following steps:
step 1: mixing a monomer and a proper amount of catalyst hypophosphorous acid in a reaction container, heating to 170-200 ℃ under the protection of inert gas, and slowly dropwise adding N-methyldiethanolamine into the reaction container;
step 2: reacting for 8-10 h at 170-200 ℃;
and step 3: step 2, adding a proper amount of alkali after the reaction is finished to keep the system neutral; adding an organic solvent for dissolving and then purifying to obtain an intermediate;
and 4, step 4: heating gamma-chloropropyltrimethylsiloxane, an intermediate, a proper amount of catalyst potassium iodide and a proper amount of solvent to 65-75 ℃; reacting in a microwave reactor for a period of time, and purifying after the reaction is finished to obtain the product;
the monomer is described by the following formula 4 or the following formula 5:
HOOC-(CH2)n-CH2-CH＝CH2
formula 4
The molar ratio of the monomer to the N-methyldiethanolamine is 2.0: 1-2.2: 1;
the molar ratio of the intermediate to the gamma-chloropropyltrimethylsiloxane is 1.0: 1-1.2: 1.
In the preparation method of the organic silicon quaternary ammonium salt, in the step 1, the using amount of hypophosphorous acid is 3-4% of the weight of the monomer; in the step 4, the dosage of the potassium iodide is 0.5 to 0.6 percent of the total weight of the gamma-chloropropyltrimethylsiloxane and the intermediate.
In the above method for preparing the organosilicon quaternary ammonium salt, the base in step 3 is KOH or NaOH, and in step 2, before the reaction is finished, the acid value of the system is controlled to be less than 3 mgKOH/g.
In the above method for preparing the organosilicon quaternary ammonium salt, in the step 3, the solvent is chloroform; in the step 4, the solvent is a mixture of isopropanol and methanol; the weight ratio of the isopropanol to the methanol is 1: 1; the amount of the solvent used was 0.5 times the weight of the intermediate.
In the preparation method of the organosilicon quaternary ammonium salt, in the step 4, the microwave power in the microwave reactor is 750W-850W; the microwave emission time is 550 min-650 min.
In the preparation method of the organosilicon quaternary ammonium salt, the purification methods in the steps 3 and 4 are obtained by performing reduced pressure rotary evaporation on the solvent.
Finally, the invention also provides an organosilicon quaternary ammonium salt emulsion, which comprises the following components:
the organosilicon quaternary ammonium salt is 20g/L as described above;
an emulsifier 1310 which is equivalent to 10-20% of the weight of the organosilicon quaternary ammonium salt;
adjusting the pH value of the system to be a proper amount of glacial acetic acid of 6-7;
the balance of water.
Compared with the prior art, the invention has the beneficial effects that:
the invention introduces gamma-chloropropyltrimethylsiloxane into the quaternary ammonium compound, and the quaternary ammonium compound is long-chain fatty acid with unsaturated groups, so that the antibacterial effect, the yellowing resistance and the softness performance and hand feeling can be achieved to a certain extent.
The principle is as follows:
(1) the gamma-chloropropyltrimethylsiloxane is introduced into the quaternary ammonium compound, reactive silicon methoxy in the product can be hydrolyzed to generate silanol which is subjected to crosslinking reaction with fabric, and can react with hydroxyl on fiber to form a covalent bond, so that the attachment performance is stronger, the safety is extremely high, the antibacterial effect is durable, and the growth of microorganisms can be effectively inhibited.
(2) The method has the advantages of high synthesis efficiency and high product purity (up to more than 95%).
(3) The C-C double bond can generate self-polymerization crosslinking to a certain degree to form a network structure, a compact film can be formed on the surface of the fabric, and the fabric has better smooth feeling and excellent softness.
(4) The presence of C ═ C double bonds can improve the yellowing resistance of the fabric to some extent.
Detailed Description
The technical solutions in the embodiments of the present invention are clearly and completely described below, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
Example 1
A preparation method of organosilicon quaternary ammonium salt comprises the following steps:
step 1: mixing a monomer and a proper amount of catalyst hypophosphorous acid in a reaction container, heating to 170-180 ℃ under the protection of inert gas, and slowly dropwise adding N-methyldiethanolamine into the reaction container; the amount of hypophosphorous acid used was 3.5% by weight based on the weight of the monomer;
the monomer is shown as formula 4 in the specification, and n is 13;
step 2: reacting for 8 hours at 170-180 ℃, and finishing the reaction when the acid value of the system is controlled to be less than 3 mgKOH/g;
and step 3: 2, after the reaction is finished, adding a proper amount of KOH to keep the system neutral, and keeping the pH value of the system at 7 +/-0.5; adding chloroform for dissolving, and performing reduced pressure rotary evaporation and purification to obtain an intermediate;
and 4, step 4: heating gamma-chloropropyltrimethylsiloxane, an intermediate, a proper amount of catalyst potassium iodide and a proper amount of solvent to 65-75 ℃; reacting in a microwave reactor for a period of time, and performing reduced pressure rotary evaporation on the solvent after the reaction is finished to obtain the product; wherein, the dosage of the potassium iodide is equivalent to 0.56 percent of the total weight of the gamma-chloropropyltrimethylsiloxane and the intermediate; the solvent is a mixture of isopropanol and methanol; the weight ratio of the isopropanol to the methanol is 1: 1; the dosage of the solvent is 0.5 time of the weight of the intermediate; in the microwave reactor, the microwave power is 800W; the microwave emission time is 10 h.
The molar ratio of the monomer to the N-methyldiethanolamine is 2: 1;
the molar ratio of the intermediate to the gamma-chloropropyltrimethylsiloxane is 1: 1.
Example 2
A preparation method of organosilicon quaternary ammonium salt comprises the following steps:
step 1: mixing a monomer and a proper amount of catalyst hypophosphorous acid in a reaction container, heating to 180-190 ℃ under the protection of inert gas, and slowly dropwise adding N-methyldiethanolamine into the reaction container; the amount of hypophosphorous acid used was 3% by weight based on the weight of the monomer;
the monomer is shown as formula 4 in the specification, and n is 14;
step 2: reacting for 10 hours at the temperature of 180-190 ℃, and finishing the reaction when the acid value of the system is controlled to be less than 3 mgKOH/g;
and step 3: 2, after the reaction is finished, adding a proper amount of KOH to keep the system neutral, and keeping the pH value of the system at 7 +/-0.5; adding chloroform for dissolving, and performing reduced pressure rotary evaporation and purification to obtain an intermediate;
and 4, step 4: heating gamma-chloropropyltrimethylsiloxane, an intermediate, a proper amount of catalyst potassium iodide and a proper amount of solvent to 70 ℃; reacting in a microwave reactor for a period of time, and performing reduced pressure rotary evaporation on the solvent after the reaction is finished to obtain the product; wherein, the dosage of the potassium iodide is equivalent to 0.56 percent of the total weight of the gamma-chloropropyltrimethylsiloxane and the intermediate; the solvent is a mixture of isopropanol and methanol; the weight ratio of the isopropanol to the methanol is 1: 1; the dosage of the solvent is 0.5 time of the weight of the intermediate; in the microwave reactor, the microwave power is 800W; the microwave emission time is 10 h.
The molar ratio of the monomer to the N-methyldiethanolamine is 2.1: 1;
the molar ratio of the intermediate to the gamma-chloropropyltrimethylsiloxane is 1.1: 1.
Example 3
A preparation method of organosilicon quaternary ammonium salt comprises the following steps:
step 1: mixing a monomer and a proper amount of catalyst hypophosphorous acid in a reaction container, heating to 190-200 ℃ under the protection of inert gas, and slowly dropwise adding N-methyldiethanolamine into the reaction container; the amount of hypophosphorous acid used was 4% by weight based on the weight of the monomer;
the monomer is shown as formula 4 in the specification, and n is 12;
step 2: reacting for 9 hours at 190-200 ℃, and finishing the reaction when the acid value of the system is controlled to be less than 3 mgKOH/g;
and step 3: 2, after the reaction is finished, adding a proper amount of KOH to keep the system neutral, and keeping the pH value of the system at 7 +/-0.5; adding chloroform for dissolving, and performing reduced pressure rotary evaporation and purification to obtain an intermediate;
and 4, step 4: heating gamma-chloropropyltrimethylsiloxane, an intermediate, a proper amount of catalyst potassium iodide and a proper amount of solvent to 75 ℃; reacting in a microwave reactor for a period of time, and performing reduced pressure rotary evaporation on the solvent after the reaction is finished to obtain the product; wherein, the dosage of the potassium iodide is equivalent to 0.6 percent of the total weight of the gamma-chloropropyltrimethylsiloxane and the intermediate; the solvent is a mixture of isopropanol and methanol; the weight ratio of the isopropanol to the methanol is 1: 1; the dosage of the solvent is 0.5 time of the weight of the intermediate; in the microwave reactor, the microwave power is 800W; the microwave emission time was 9.5 h.
The molar ratio of the monomer to the N-methyldiethanolamine is 2.2: 1;
the molar ratio of the intermediate to the gamma-chloropropyltrimethylsiloxane is 1.2: 1.
Example 4
Substantially the same as in example 1, except that: the monomers are selected as shown in formula 5 of the specification, wherein n is 13.
Example 5
Substantially the same as in example 1, except that: the monomers are selected as shown in formula 5 of the specification, wherein n is 12.
Example 6
Substantially the same as in example 1, except that: the monomers are selected as shown in formula 5 of the specification, wherein n is 14.
Comparative example 1
Substantially the same as in example 1, except that: the monomer is selected as shown in the following formula 6, wherein n is 13.
HOOC-(CH2)n-CH2-CH2-CH3
Application example 1
An organosilicon quaternary ammonium salt emulsion is prepared as a fabric softener, and the formula is as follows:
the organosilicon quaternary ammonium salt as in example 1 is 20 g/L;
emulsifier 1310 (isomeric alcohol polyoxyethylene ether) corresponding to 15% of the weight of the organosilicon quaternary ammonium salt;
adjusting the pH value of the system to be a proper amount of glacial acetic acid of 6-7;
the balance of water.
Application example 2
An organosilicon quaternary ammonium salt emulsion is prepared as a fabric softener, and the formula is as follows:
the organosilicon quaternary ammonium salt as in example 2 is 20 g/L;
emulsifier 1310 in an amount corresponding to 10% by weight of the silicone quaternary ammonium salt;
adjusting the pH value of the system to be a proper amount of glacial acetic acid of 6-7;
the balance of water.
Application example 3
An organosilicon quaternary ammonium salt emulsion is prepared as a fabric softener, and the formula is as follows:
the organosilicon quaternary ammonium salt as in example 3 is 20 g/L;
emulsifier 1310 in an amount corresponding to 20% by weight of the silicone quaternary ammonium salt;
adjusting the pH value of the system to be a proper amount of glacial acetic acid of 6-7;
the balance of water.
Application example 4
An organosilicon quaternary ammonium salt emulsion is prepared as a fabric softener, and the formula is as follows:
the organosilicon quaternary ammonium salt as in example 4 is 20 g/L;
emulsifier 1310 (isomeric alcohol polyoxyethylene ether) corresponding to 15% of the weight of the organosilicon quaternary ammonium salt;
adjusting the pH value of the system to be a proper amount of glacial acetic acid of 6-7;
the balance of water.
Application example 5
An organosilicon quaternary ammonium salt emulsion is prepared as a fabric softener, and the formula is as follows:
the organosilicon quaternary ammonium salt as in example 5 is 20 g/L;
emulsifier 1310 (isomeric alcohol polyoxyethylene ether) corresponding to 15% of the weight of the organosilicon quaternary ammonium salt;
adjusting the pH value of the system to be a proper amount of glacial acetic acid of 6-7;
the balance of water.
Application example 6
An organosilicon quaternary ammonium salt emulsion is prepared as a fabric softener, and the formula is as follows:
the organosilicon quaternary ammonium salt as in example 6 is 20 g/L;
emulsifier 1310 (isomeric alcohol polyoxyethylene ether) corresponding to 15% of the weight of the organosilicon quaternary ammonium salt;
adjusting the pH value of the system to be a proper amount of glacial acetic acid of 6-7;
the balance of water.
Application comparative example 1
An organosilicon quaternary ammonium salt emulsion is prepared as a fabric softener, and the formula is as follows:
silicone quaternary ammonium salt as in comparative example 120 g/L;
emulsifier 1310 in an amount of 15% by weight of the silicone quaternary ammonium salt;
adjusting the pH value of the system to be a proper amount of glacial acetic acid of 6-7;
the balance of water.
Comparative application example 2
D1821:20g/L；
15% by weight of emulsifier 1310 corresponding to D1821;
adjusting the pH value of the system to be a proper amount of glacial acetic acid of 6-7;
the balance of water.
Comparative application example 3
The same as in application example 1, except that the emulsifier used was AEO-3 (fatty alcohol polyoxyethylene ether);
application comparative example 4
The same as in application example 1, except that NP-10P (nonylphenol polyoxyethylene ether phosphate) was used as the emulsifier;
comparative application example 5
The same as in application example 1, except that the emulsifier used was TX-10 (octylphenol polyvinyl chloride ether) FF1B
The preparation methods of the above application examples 1 to 6 and application comparative examples 1 to 5 are as follows:
accurately weighing organosilicon quaternary ammonium salt (or D1821), adding emulsifier, stirring for 5 minutes, then adding glacial acetic acid, stirring for 5 to 10 minutes at a stirring speed of 500 to 2000 revolutions per minute, keeping the stirring speed unchanged, then adding water, continuously stirring for 60 minutes, ending stirring, and standing until the mixture is completely clear to obtain the light yellow transparent microemulsion.
Fabric finishing method
Firstly, carrying out soaking-rolling treatment on original white gray cloth in emulsion (the cloth bath ratio is 1:20, soaking is carried out in water bath at 65 ℃ for 30min, and the rolling residual rate is 70% (the water content accounts for the mass of the cloth)); then taking out the cloth, drying the cloth at 80 ℃ for 120s, and curing and shaping the cloth at 130 ℃ for 90 s; finally, the cloth is put in the air to be balanced for 24 hours.
Application testing method
And (3) testing the whiteness and the softness of the finished fabric:
① whiteness analysis
The test was carried out using an SBDY-1 digital whiteness tester.
② softness test
The sample is cut into a square of 12 x 12cm, the operation method is carried out according to the national standard GB/T-8942-2002, the cloth-bath ratio is 1:20, the sample concentration is 50g/L, and the test is carried out by using an RH-R/100 type computer softness tester.
And (3) testing the antibacterial performance of the finished fabric:
the bacteriostatic loop method belongs to qualitative detection, and has the advantages of high detection speed, simpler experimental steps and low cost. And (3) roughly measuring the concentration of the bacterial suspension by a spectrophotometric method at the early stage and preparing a solid culture medium. Cutting a clean cloth sample into square woven cloth with the length of 12 x 12cm, rinsing and desizing the woven cloth with distilled water for 3 times, naturally airing the woven cloth for later use, adding a proper amount of an emulsifying agent into a certain amount of organic silicon quaternary ammonium salt for emulsification, putting the cloth sample into each emulsion (the cloth-bath ratio is 1:20) for finishing, drying and sterilizing the cloth for later use. A circular cloth of 2cm diameter was cut out and the cloth was placed between solid agar media coated with bacteria with tweezers. Culturing at 37 deg.C for 24h, checking whether bacteria are propagated at the bottom of the fabric, measuring the diameter of the zone, calculating the zone size, and comparing to determine its antibacterial property.
Test results
And (3) softness testing:
table 1 shows the results of the softness test in application examples 1 to 6 and application comparative examples 1 to 2
Table 1 softness test results
The following conclusions can be drawn from the test results of table 1:
1. the softness of application examples 4-6 was superior to that of application examples 1-3, indicating that the F substitution is favorable for improvement of softness;
2. the softness of application examples 1-3 is superior to that of application comparative example 1, illustrating that the self-polymerization product due to C ═ C unsaturated bond at the tail of R group contributes to improvement of softness;
3. the softness of application examples 1-3 is better than that of application comparative example 1, and the softness of application comparative example 1 is similar to that of application comparative example 2, indicating that C ═ C unsaturated bonds can make the softness of the product better than that of D1821.
And (3) whiteness testing:
table 2 shows the results of whiteness tests of application examples 1 to 6 and application comparative examples 1 to 2
Table 2 whiteness test results
The following conclusions can be drawn from the above tests:
1. the whiteness of application examples 4-6 was superior to application examples 1-3, indicating that F substitution is beneficial to whiteness improvement;
2. the whiteness of application examples 1-3 was superior to that of application comparative example 1, illustrating that the self-polymerization product due to the C ═ C unsaturated bond at the tail of the R group is favorable for the improvement of whiteness;
3. the whiteness of application examples 1-3 is better than that of application comparative example 1, and the whiteness of application comparative example 1 is similar to the softness of application comparative example 2, which shows that unsaturated bonds C ═ C can make the whiteness of the product better than that of D1821.
Antibacterial property test
The antibacterial properties of application examples 1 to 6 and application comparative example 1 were similar.
Emulsion stability test
At normal temperature, the emulsion system is unstable in application examples 1 to 6 and application comparative examples 1 to 5.
In the case of increasing the emulsification temperature to 60 ℃, stable emulsions could be formed using examples 1 to 6 and comparative examples 1 to 2, and stable emulsions could not be formed using comparative examples 3 to 5.
Through the above tests, we have found that by introducing gamma-chloropropyltrimethylsiloxane into a quaternary ammonium compound, which is a long-chain fatty acid with an unsaturated group, it is possible to improve yellowing resistance, and achieve excellent soft expression properties and hand.
Further, by introducing an F substituent, yellowing resistance and soft expression properties and hand can be further improved.
It will be evident to those skilled in the art that the invention is not limited to the details of the foregoing illustrative embodiments, and that the present invention may be embodied in other specific forms without departing from the spirit or essential attributes thereof. The present embodiments are therefore to be considered in all respects as illustrative and not restrictive, the scope of the invention being indicated by the appended claims rather than by the foregoing description, and all changes which come within the meaning and range of equivalency of the claims are therefore intended to be embraced therein.
Claims (10)
1. A quaternary ammonium salt of organosilicon for improving whiteness and softness of fabrics, which is characterized in that: the structural formula of the organosilicon quaternary ammonium salt is as follows:
wherein R is unsaturated fatty group of C15-C17 or unsaturated fatty group of C15-C17 substituted by fluorine.
2. The quaternary ammonium silicone salt for improving whiteness and softness of fabrics according to claim 1, wherein the quaternary ammonium silicone salt has the following structural formula:
wherein n in the formulas 2 and 3 is 12-14.
3. The quaternary ammonium silicone salt for improving whiteness and softness of fabrics according to claim 2, wherein n is 13.
4. A method for preparing the quaternary ammonium silicone salt according to claim 2 or 3, comprising the steps of:
step 1: mixing a monomer and a proper amount of catalyst hypophosphorous acid in a reaction container, heating to 170-200 ℃ under the protection of inert gas, and slowly dropwise adding N-methyldiethanolamine into the reaction container;
step 2: reacting for 8-10 h at 170-200 ℃;
and step 3: step 2, adding a proper amount of alkali after the reaction is finished to keep the system neutral; adding an organic solvent for dissolving and then purifying to obtain an intermediate;
and 4, step 4: heating gamma-chloropropyltrimethylsiloxane, an intermediate, a proper amount of catalyst potassium iodide and a proper amount of solvent to 65-75 ℃; reacting in a microwave reactor for a period of time, and purifying after the reaction is finished to obtain the product;
the monomer is described by the following formula 4 or the following formula 5:
HOOC-(CH2)n-CH2-CH＝CH2
formula 4
The molar ratio of the monomer to the N-methyldiethanolamine is 2.0: 1-2.2: 1;
the molar ratio of the intermediate to the gamma-chloropropyltrimethylsiloxane is 1.0: 1-1.2: 1.
5. The method for preparing the organosilicon quaternary ammonium salt according to claim 4, wherein in the step 1, the amount of hypophosphorous acid is 3-4% of the weight of the monomer; in the step 4, the dosage of the potassium iodide is 0.5 to 0.6 percent of the total weight of the gamma-chloropropyltrimethylsiloxane and the intermediate.
6. The method for preparing organosilicon quaternary ammonium salt according to claim 4, wherein the base in step 3 is KOH or NaOH, and the acid value of the system is controlled to be < 3mgKOH/g before the reaction is completed in step 2.
7. The method for preparing quaternary ammonium salt of organosilicon according to claim 4, wherein in step 3, the solvent is chloroform; in the step 4, the solvent is a mixture of isopropanol and methanol; the weight ratio of the isopropanol to the methanol is 1: 1; the amount of the solvent used was 0.5 times the weight of the intermediate.
8. The method for preparing organosilicon quaternary ammonium salt according to claim 4, wherein in the step 4, microwave power in a microwave reactor is 750W-850W; the microwave emission time is 550 min-650 min.
9. The method for preparing organosilicon quaternary ammonium salt according to claim 4, wherein the purification method in step 3 and step 4 is performed by rotary evaporation of solvent under reduced pressure.
10. The organosilicon quaternary ammonium salt emulsion is characterized by comprising the following components:
the quaternary ammonium silicone salt of any one of claims 1 to 3, in an amount of 20 g/L;
an emulsifier 1310 which is equivalent to 10-20% of the weight of the organosilicon quaternary ammonium salt;
adjusting the pH value of the system to be a proper amount of glacial acetic acid of 6-7;
the balance of water.
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Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH06279371A (en) * | 1993-03-31 | 1994-10-04 | Nitto Chem Ind Co Ltd | Production of unsaturated quaternary ammonium salt |
| CN103044480A (en) * | 2012-12-26 | 2013-04-17 | 广州大学 | Method for preparing ester organosilicon quaternary ammonium salt |
| CN106188124A (en) * | 2016-07-12 | 2016-12-07 | 皖西学院 | The preparation method of novel ester organosilicon quaternary ammonium salt |
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Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH06279371A (en) * | 1993-03-31 | 1994-10-04 | Nitto Chem Ind Co Ltd | Production of unsaturated quaternary ammonium salt |
| CN103044480A (en) * | 2012-12-26 | 2013-04-17 | 广州大学 | Method for preparing ester organosilicon quaternary ammonium salt |
| CN106188124A (en) * | 2016-07-12 | 2016-12-07 | 皖西学院 | The preparation method of novel ester organosilicon quaternary ammonium salt |
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