CN108166257B

CN108166257B - Mercerizing penetrating agent and preparation method thereof

Info

Publication number: CN108166257B
Application number: CN201611117594.XA
Authority: CN
Inventors: 李成棣; 何志强; 方洇; 常石磊
Original assignee: Shanghai Dongda Chemical Co Ltd
Current assignee: Shanghai Dongda Chemical Co Ltd
Priority date: 2016-12-07
Filing date: 2016-12-07
Publication date: 2019-12-31
Anticipated expiration: 2036-12-07
Also published as: CN108166257A

Abstract

The invention discloses a mercerizing penetrating agent and a preparation method thereof. Which comprises the following components: 20-30 wt% of silicon modified polyether, 10-20 wt% of fatty alcohol-polyoxyethylene ether sulfate, 10-20 wt% of alkyl diphenyl ether sulfonate and the balance of water; the number average molecular weight of the silicon modified polyether is 200-2000 g/mol, and the structural general formula is as follows: r is straight-chain or branched C₆～C₁₈R' is "straight-chain or branched C₁～C₁₀Alkylene of "or C₆～C₁₀The arylene group of (a) is 1 to 20, n is 0 to 20, and m or n is an integer. The preparation method of the penetrant is simple and convenient; the components have mutual synergistic effect, so that the alkali resistance of the product reaches 300g/L, and the product has good permeability and alkali resistance stability in an alkali solution of 180-300 g/L; and the method also has extremely low foam, does not influence the recovery of alkali liquor, and obviously improves the mercerizing effect.

Description

Mercerizing penetrating agent and preparation method thereof

Technical Field

The invention relates to a mercerizing penetrating agent and a preparation method thereof.

Background

Mercerizing refers to a treatment process of treating cotton products (yarns and fabrics) with concentrated caustic soda solution under the condition of tension and then washing off caustic soda under the tension; the method can improve the adsorption property, the glossiness and the dimensional stability of the fabric, and is an important link in the dyeing and finishing pretreatment of the fabric. In order to improve the quality of mercerized products and obtain uniform mercerizing effect, a mercerizing assistant, such as a penetrating agent, is added into mercerizing liquid. In mercerizing and finishing, the concentration of caustic soda is generally higher than 180g/L, the caustic soda is viscous at low temperature, the permeability of alkali liquor is reduced due to severe contraction of cotton and hemp fibers in a short mercerizing process time, so that the effect of surface mercerizing can be achieved only, and a penetrating agent in the prior art is poor in alkali resistance and cannot penetrate into fibers such as cotton fabrics and the like quickly.

Penetrants are surfactants that enable liquid to quickly and uniformly penetrate into a solid substance, and are widely used in textile, paper making, printing ink, pesticides, and other fields. For example, in textile printing and dyeing production, penetrants have a wide range of uses, such as desizing, scouring, bleaching, wetting or dispersing of dyes, dyeing, sizing, and resin finishing. Penetrants are generally classified into nonionic penetrants, anionic penetrants, complex penetrants, and the like, according to the ionic classification, and amphoteric and cationic penetrants are rarely used.

Wherein, the nonionic penetrating agent (such as fatty alcohol-polyoxyethylene ether, JFC for short) is difficult to be applied to the mercerizing process due to the strong influence of cloud point and foamability. The anionic penetrant has good permeability but strong foamability; the traditional anionic penetrant dioctyl sodium sulfosuccinate (OT for short) has the defects of poor heat resistance, low permeation speed and strong foamability, and is difficult to meet the requirements of mercerization process, and particularly, the existence of foam brings inconvenience to the technical processes of textile printing and dyeing and the like, such as influence on operation, efficiency reduction, water consumption increase and the like. To solve the foaming problem, people have long searched for and put forward various solutions.

Chinese patent document CN102011317A discloses an alkali-resistant wet cloth mercerizing penetrating agent and a preparation method thereof, wherein the penetrating agent is isomeric tridecanol polyoxyethylene ether phosphate, and can be used for wet cloth mercerizing processes of cotton fabrics, linen fabrics and blended fabrics thereof. Chinese patent document CN103352366A discloses an alkali-resistant penetrating agent for mercerizing cotton fabrics, which mainly comprises fatty alcohol ether sulfate. Although the alkyl phosphate or alkyl sulfate has strong alkali resistance and good permeability, the alkyl phosphate or alkyl sulfate is easy to foam, the existence of foam brings inconvenience to the mercerization and other processes, such as operation influence, efficiency reduction, water consumption increase and the like, and alkali liquor after mercerization is difficult to recover, so that the production cost is increased, and the pressure on the environment is caused. Chinese patent document CN102503973A discloses a preparation method of a strong alkali-resistant mercerizing penetrant ethylene glycol monobutyl ether phosphate, although the penetrant does not generate ammonia smell and foam and does not influence alkali liquor recovery, the penetrant contains phosphate components, and if a large amount of the product is used, water eutrophication is caused. This problem is urgently needed to be solved.

Disclosure of Invention

The invention solves the technical problems that the penetrant for mercerization is easy to foam, the existence of foam brings inconvenience to the mercerization and other technological processes, and alkali liquor after mercerization is difficult to recover, so that the production cost is increased, and the pressure is caused to the environment; and the phosphate penetrant contains phosphate components, and if a large amount of the product is used, the defect of water eutrophication can be caused, so that the mercerizing penetrant and the preparation method thereof are provided. The preparation method of the penetrant is simple and convenient and easy to operate. The penetrant of the invention can be free of phosphorus element and/or APEO, and is environment-friendly; the components have mutual synergistic effect, so that the alkali resistance (NaOH solution) of the penetrant of the invention reaches 300g/L, the penetrant has good permeability in 180-300 g/L NaOH solution, and the alkali resistance stability is good; and the method also has extremely low foam, does not influence the recovery of alkali liquor, and can obviously improve the mercerizing effect.

The invention solves the technical problems through the following technical scheme.

The invention provides a mercerizing penetrating agent which comprises the following components: 20-30 wt% of silicon modified polyether, 10-20 wt% of fatty alcohol-polyoxyethylene ether sulfate, 10-20 wt% of alkyl diphenyl ether sulfonate and the balance of water;

the number average molecular weight of the silicon modified polyether is 200-2000 g/mol, and the structural general formula is shown as formula I:

r is straight-chain or branched C₆～C₁₈R' is "straight-chain or branched C₁～C₁₀Alkylene of "or C₆～C₁₀The arylene group of (a) is 1 to 20, n is 0 to 20, and m or n is an integer.

In the present invention, the mercerizing penetrating agent preferably consists of the following components: 20-30 wt% of silicon modified polyether, 10-20 wt% of fatty alcohol-polyoxyethylene ether sulfate, 10-20 wt% of alkyl diphenyl ether sulfonate and the balance of water.

In the present invention, the raw material components of the penetrating agent preferably do not contain phosphorus element and/or alkylphenol polyoxyethylene ether compound (APEO for short).

In the present invention, the number average molecular weight of the silicon-modified polyether is preferably 363 to 900g/mol, more preferably 436 to 834g/mol, and most preferably 512g/mol, 580g/mol, 594g/mol or 744 g/mol.

In the present invention, R is preferably a straight-chain or branched C₈～C₁₅Alkyl of (2), more preferably branched C₈～C₁₅Alkyl of (2), most preferably branched C₈Alkyl, branched C of₁₀Alkyl or branched C of₁₃Alkyl group of (1). In a specific embodiment of the present invention, said C of the branched chain₈The alkyl group of (A) is preferably 6-methyl-1-heptanol or EXXAL^TM8 the hydroxyl group is removed. C of said branched chain₁₀The alkyl group of (A) is preferably EXXAL^TM10 the hydroxyl moiety is removed. C of said branched chain₁₃The alkyl group of (A) is preferably EXXAL^TM13 the hydroxyl group is removed. Wherein the 6-methyl-1-heptanol (CAS number 26952-21-6) and the EXXAL^TM8(CAS number 68526-83-0) are all isooctanols. The EXXAL^TM10(CAS number 68526-85-2) is isomeric dodecanols. The EXXAL^TM13(CAS number 68526-86-3) is the isomeric tridecanols. The EXXAL^TM8. The EXXAL^TM10 and the EXXAL^TM13 are all commercial products of exxonmobil chemical company.

In the present invention, the alkylene group may be an alkylene group conventionally understood in the art, and is generally an alkylene group in which two monovalent atoms or groups are formally eliminated from an alkyl group, and the remainder is referred to as an alkylene group. The arylene group can be a arylene group as is conventionally understood in the art, and is typically an aromatic group formally interrupted by two monovalent atoms or groups, the remainder being referred to as arylene.

In the present invention, R' is preferably "straight-chain or branched C₁～C₆Alkylene of "or C₆～C₇More preferably "straight or branched C₁～C₃An alkylene group of,The straight chain or branched C₁～C₃The alkylene group of (A) may be conventional in the art, preferably-CH₂-、or-CH₂CH₂CH₂-。

In the present invention, m is preferably an integer of 3 to 15, more preferably an integer of 5 to 10, and most preferably 7 or 9.

In the present invention, n is preferably an integer of 0 to 10, and more preferably 2.

In the present invention, the preparation method of the silicon modified polyether can be conventional in the art, and preferably comprises the following steps: (1) under the anaerobic condition, polyether and organic alkali are mixed and react to obtain a mixture; wherein the reaction temperature is 80-140 ℃; the organic base is sodium methoxide and/or potassium methoxide; the feeding molar ratio of the organic base to the polyether is (1.0-1.5): 1; the structural general formula of the polyether is shown as formula II:

r is straight-chain or branched C₆～C₁₈The alkyl group of (1) is 1-20, n is 0-20, and m or n are integers;

(2) cooling the mixture obtained in the step (1), and mixing the mixture with halogenated alkyl trimethyl silane for reaction to obtain the silicon modified polyether; wherein the reaction temperature is 60-120 ℃; the feeding molar ratio of the halogenated alkyl trimethylsilane to the polyether is (1.0-1.4): 1; the structural general formula of the halogenated alkyl trimethylsilane is shown as the formula III:

Si(CH₃)₃-R' -X formula III

Wherein R' is "straight or branched C₁～C₁₀Alkylene of "or C₆～C₁₀And X is a halogen element.

In step (1), the oxygen-free atmosphere may be conventional in the art, and is preferably nitrogen and/or argon.

In step (1), the polyether may be a polyether conventionally used in the art and corresponding to the above general structural formula of formula II. The polyethers can be prepared by methods conventional in the art, preferably by the following steps: under an oxygen-free atmosphere, firstly dripping ethylene oxide into a mixture containing initiator alcohol and a catalyst, carrying out a first ring-opening polymerization reaction and a first curing reaction, then dripping propylene oxide, and carrying out a second ring-opening polymerization reaction and a second curing reaction to obtain the catalyst; wherein the initiator alcohol is a straight chain or branched chain C₆～C₁₈The molar ratio of the ethylene oxide to the initiator alcohol is (1-20): 1, the molar ratio of the propylene oxide to the initiator alcohol is (0-20): 1.

Wherein the oxygen-free atmosphere may be conventional in the art, preferably nitrogen and/or argon.

Wherein the catalyst and the initiator alcohol are preferably pretreated before the ring-opening polymerization reaction. The pretreatment may be a pretreatment operation conventional in the art, and is preferably performed as follows: and dehydrating the catalyst and the initiator alcohol for 25-35 min at the temperature of 105-115 ℃ and the pressure of-0.095-0.085 MPa in an oxygen-free atmosphere. More preferably, the method comprises the following steps: dehydrating the catalyst and the initiator alcohol at 110 ℃ and-0.09 MPa for 30min in an oxygen-free atmosphere.

Wherein the catalyst can be strong basic catalyst conventionally used in the field, preferably KOH, NaOH, KOCH₃And NaOCH₃One or more of (a). The amount of the catalyst may be as conventional in the art, preferably 0.05 to 1 wt% of the amount of the starter alcohol, more preferably 0.15 to 0.4 wt% of the amount of the starter alcohol, most preferably 0.2 wt%, 0.25 wt%, 0.3 wt% or 0.35 wt% of the amount of the starter alcohol.

Wherein, the initiator alcohol can be the conventional one in the field, and can prepare the polyether with the structural general formula of formula II, preferably the linear or branched C₈～C₁₅Alkyl of (2), more preferably branched C₈～C₁₅Alkyl of (2), most preferably branched C₈Alkyl, branched C of₁₀Alkyl or branched C of₁₃Alkyl group of (1). In a specific embodiment of the invention, C of said branch₈The alkyl group of (A) is preferably 6-methyl-1-heptanol (CAS number 26952-21-6) or EXXAL^TM8(CAS number 68526-83-0). C of said branch chain₁₀The alkyl group of (A) is preferably EXXAL^TM10(CAS number 68526-85-2). C of said branch chain₁₃The alkyl group of (A) is preferably EXXAL^TM13(CAS number 68526-86-3). Wherein the 6-methyl-1-heptanol and the EXXAL^TM8 are all isooctanols. The EXXAL^TM10 is isomeric dodecanol. The EXXAL^TM13 is isomeric tridecanol. The EXXAL^TM8. The EXXAL^TM10 and the EXXAL^TM13 are all commercial products of exxonmobil chemical company.

Wherein the temperature of the first ring-opening polymerization reaction and the second ring-opening polymerization reaction can be conventional in the art, and is preferably 120-160 ℃, more preferably 130-150 ℃, and most preferably 135 ℃, 140 ℃ or 145 ℃. The pressure of the first ring-opening polymerization reaction and the second ring-opening polymerization reaction can be conventional in the art, and is preferably independently 0.05 to 0.35MPa, more preferably independently 0.2 to 0.3MPa, and most preferably independently 0.25 MPa. The temperature and pressure of the first aging reaction and the second aging reaction are the same as those of the "first ring-opening polymerization reaction or the" second ring-opening polymerization reaction ". The time of the first curing reaction and the second curing reaction can be conventional in the art, and is preferably independently 25-35 min, and more preferably independently 30 min.

Wherein the molar ratio of the ethylene oxide to the starter alcohol is preferably (3-15): 1, more preferably (5-10): 1, optimally 7: 1 or 9: 1. the molar ratio of the ethylene oxide to the starter alcohol is m in the polyether formula or modified polyether formula, as is common in the art: 1.

wherein the molar ratio of the propylene oxide to the initiator alcohol is preferably (2-10): 1. The molar ratio of the propylene oxide to the starter alcohol is n in the polyether formula or modified polyether formula: 1.

in the step (1), the reaction temperature is preferably 100 to 120 ℃, more preferably 105 to 115 ℃, and most preferably 110 ℃.

In the step (1), the reaction time may be conventional in the art, preferably 2 to 10 hours, more preferably 5 to 8 hours, and most preferably 6 to 7 hours.

In step (1), the pressure of the reaction can be conventional in the art, and is preferably-0.08 to-0.095 MPa, and more preferably-0.09 MPa. Under negative pressure, methanol generated in the reaction process can be removed.

In the step (1), the feeding molar ratio of the alkali to the polyether is preferably 1.15-1.3: 1, more preferably 1.25: 1.

in the step (2), the temperature after cooling may be conventional in the art, and generally is below the boiling point of the haloalkyl trimethylsilane, preferably 40 to 60 ℃, more preferably 45 to 50 ℃.

In step (2), the haloalkyltrimethylsilane may be a haloalkyltrimethylsilane which is conventional in the art, and is preferably chloroalkyltrimethylsilane, bromoalkyltrimethylsilane or iodoalkyltrimethylsilane. Among them, the chloroalkyltrimethylsilane may be conventional in the art, and is preferably chloromethyltrimethylsilane (CAS number 2344-80-1), 1-chloroethyltrimethylsilane (CAS number 7787-87-3), γ -chloropropyltrimethylsilane (CAS number 2344-83-4), (2-chlorobenzyl) -trimethylsilane (CAS number 68307-67-5), or p-chlorophenyltrimethylsilane (CAS number 10557-71-8).

In the step (2), the reaction temperature is preferably 80 to 110 ℃, more preferably 85 to 105 ℃, and most preferably 90 ℃, 95 ℃ or 100 ℃.

In the step (2), the reaction time is preferably 2 to 8 hours, more preferably 4 to 6 hours, and most preferably 4.5 hours, 5 hours, or 5.5 hours.

In the step (2), the reaction pressure is preferably 0 to 0.5MPa, more preferably 0.1 to 0.2MPa, and most preferably 0.15 MPa.

In the step (2), the feeding molar ratio of the haloalkyl trimethylsilane to the polyether is preferably (1.05-1.2): 1, more preferably (1.1 to 1.15): 1.

preferably, the mixture after the mixing reaction in the step (2) is subjected to a post-treatment operation. The work-up may be carried out by purification operations conventional in the art, preferably as follows: and (3) cooling the mixture obtained after the mixing reaction in the step (2) to 60-80 ℃, adjusting the pH value to 4.0-5.0, adsorbing with an adsorbent, dehydrating, and filtering to obtain the catalyst.

Wherein the temperature after cooling is preferably 65 to 75 ℃, more preferably 70 ℃.

Wherein the pH value is preferably 4.5.

Wherein, the pH value regulator for regulating the pH value can be conventional in the field, and is preferably phosphoric acid. The concentration of the pH adjusting agent may be conventional in the art and is typically 85 wt%.

The adsorbent can be an adsorbent which can adsorb salts and is conventional in the field, and preferably magnesium silicate. The amount of the adsorbent can be conventional in the art, and is preferably 0.5 to 5% of the total weight of the mixture after the mixing reaction in step (2), more preferably 1 to 3% of the total weight of the mixture after the mixing reaction in step (2), and most preferably 1.5%, 2%, or 2.5% of the total weight of the mixture after the mixing reaction in step (2).

Wherein, the operation and conditions of the dehydration can be the operation and conditions conventional in the field, and the water is removed by reduced pressure distillation. The filtration operations and conditions may be those conventional in the art.

In the invention, the fatty alcohol polyoxyethylene ether sulfate (AES for short) can be fatty alcohol polyoxyethylene ether sulfate which is conventional in the field. In the fatty alcohol polyoxyethylene ether sulfate, the number of carbon atoms of fatty alcohol is preferably 8-14, and more preferably 10, 12 or 13; the ethylene oxide number (EO number) is preferably 3 to 4.

In the invention, the dosage of the fatty alcohol-polyoxyethylene ether sulfate is preferably 15-18 wt%.

In the present invention, the alkyl diphenyl oxide sulfonate may be an alkyl diphenyl oxide sulfonate which is conventional in the art, preferably a sodium salt of alkyl diphenyl oxide sulfonate, more preferably sodium dodecyl diphenyl oxide sulfonate, sodium decyl diphenyl oxide sulfonate, sodium octyl diphenyl oxide sulfonate or sodium hexadecyl diphenyl oxide sulfonate. In the alkyl diphenyl oxide sulfonate, the number of carbon atoms of the alkyl group is preferably 8 to 16, more preferably 10 to 12.

In the present invention, the amount of the alkyl diphenyl oxide sulfonate is preferably 14 to 15%.

In the present invention, the water may be water conventional in the art, and preferably deionized water.

The preparation method of the penetrant described in the invention can be conventional in the field, and can be realized by uniformly mixing the components according to the conventional method in the field.

The invention also provides a preparation method of the penetrant, which comprises the following steps: and (2) uniformly mixing the silicon modified polyether, the fatty alcohol-polyoxyethylene ether sulfate and the alkyl diphenyl ether sulfonate mixture with the water, and then adjusting the pH value to 6-8 to obtain the modified polyether.

In the present invention, the mixture can be prepared by a method conventional in the art, preferably by the following steps: stirring and mixing for 20-40 min at normal pressure and room temperature; more preferably by the steps of: stirring and mixing for 30min at room temperature and normal pressure. Wherein the room temperature can be conventional in the field, and is generally 20-30 ℃. The operation and conditions of the stirring and mixing may be those conventional in the art.

In the present invention, the operation and conditions of the mixing may be those conventional in the art. The mixing time can be conventional in the art, and is preferably 20-40 min, and more preferably 30 min.

In the present invention, the operation of adjusting the pH value can be conventional in the art, and is generally performed by using NaOH. The pH is preferably 7.

On the basis of the common knowledge in the field, the above preferred conditions can be combined randomly to obtain the preferred embodiments of the invention.

The starting materials used in the present invention are commercially available unless otherwise specified.

The positive progress effects of the invention are as follows:

the preparation method of the penetrant is simple and convenient and easy to operate. The penetrant of the invention can be free of phosphorus element and/or APEO, and is environment-friendly; the components have mutual synergistic effect, so that the alkali resistance (NaOH solution) of the penetrant of the invention reaches 300g/L, the penetrant has good permeability in 180-300 g/L NaOH solution, and the alkali resistance stability is good; and the method also has extremely low foam, does not influence the recovery of alkali liquor, and can obviously improve the mercerizing effect.

Drawings

FIG. 1 is an infrared spectrum of the silicon-modified polyether and polyether of example 1, wherein a is an infrared spectrum of the polyether and b is an infrared spectrum of the silicon-modified polyether.

Detailed Description

The invention is further illustrated by the following examples, which are not intended to limit the scope of the invention. The experimental methods without specifying specific conditions in the following examples were selected according to the conventional methods and conditions, or according to the commercial instructions.

The raw materials used in the following examples and comparative examples are all commercially available products unless otherwise specified. Wherein 6-methyl-1-heptanol (CAS number 26952-21-6) and EXXAL^TM8(CAS number 68526-83-0) are all isooctanols; EXXAL^TM10(CAS number 68526-85-2) is isomeric dodecanol; EXXAL^TM13(CAS number 68526-86-3) is isomeric tridecanols; EXXAL^TM8、EXXAL^TM10 and EXXAL^TM13 are all commercially available products of exxonmobil chemical; the fatty alcohol polyoxyethylene ether sulfate is a product sold in Zhejiang Zanyu, and the alkyl diphenyl ether sulfonate is a product sold in Dow chemical market.

Example 1

TABLE 1

The formulation of each raw material component of the penetrant of this example is shown in table 1. Wherein the alkyl diphenyl ether sulfonate is sodium octyl diphenyl ether sulfonate; the fatty alcohol polyoxyethylene sulfate is isomeric decyl alcohol polyoxyethylene ether sulfate (EO number is 3);

preparation of silicon-modified polyether:

(1) preparation of polyether: in a pressure reactor, 100 parts of isomeric tridecanol (EXXAL) are added^TM13) And KOCH₃(the dosage of the water solution is 0.2 percent of the weight of the isomeric tridecanol), replacing the air in the kettle with nitrogen for 3 times, heating to 110 ℃, and dehydrating for 30min under the vacuum degree environment of-0.09 MPa or less. Heating to 120 ℃, slowly dripping ethylene oxide (the molar ratio of the ethylene oxide to the isomeric tridecanol is 9: 1), carrying out ring-opening polymerization reaction under the conditions that the pressure is 0.2MPa and the temperature is 140 ℃, and curing for 30min after dripping the ethylene oxide to obtain polyether; the general structural formula is shown as follows:

wherein R-O-is isomeric tridecanol (EXXAL)^TM13) And (3) dehydrogenizing the part, wherein m is 9 and n is 0.

The hydroxyl value [ I (OH) (mg/g) ] of the synthesized polyether was determined according to the method of GB/T7383-2007 by using the formula (1): (56.1X 1000)/I (OH), the molecular weight of the polyether was calculated to be 596 g/mol.

(2) Adding 100 parts of polyether and sodium methoxide prepared in the step (1) into a pressure reaction kettle, introducing nitrogen, vacuumizing and replacing for 3 times, and mixing and reacting to obtain a mixture; wherein the reaction temperature is 110 ℃, the pressure is-0.095 MPa (under the vacuum condition, methanol generated by the reaction can be removed), and the reaction time is 6.5 h; the feeding molar ratio of sodium methoxide to polyether is 1.15;

(3) cooling the mixture obtained in the step (2) to 50 ℃, and then dropwise adding chloromethyl trimethylsilane (structural general formula Si (CH)₃)₃-CH₂-Cl) to carry out mixing reaction to obtain a silicon modified polyether crude product; wherein the reaction temperature is 105 ℃, the pressure is 0.2MPa, and the reaction time is 5 h; the feeding molar ratio of chloromethyl trimethylsilane to polyether is 1.1: 1;

(4) cooling the crude silicon modified polyether product to 75 ℃, adding 85 wt% of phosphoric acid to neutralize until the pH value is 5, adding 2 wt% of adsorbent magnesium silicate (the percentage is the percentage of the adsorbent in the total weight of the crude product) to adsorb, then carrying out reduced pressure distillation dehydration, and filtering to obtain the refined silicon modified polyether, wherein the number average molecular weight is 744g/mol, and the structural general formula is as follows:

wherein R-O-is isomeric tridecanol (EXXAL)^TM13) Dehydrogenated moieties, R' being-CH₂-，m＝9，n＝0。

FIG. 1 is an infrared spectrum of the silicon-modified polyether and polyether of example 1, wherein a is an infrared spectrum of the polyether and b is an infrared spectrum of the silicon-modified polyether. As can be seen from comparison of FIG. b with FIG. a, the distance from 1260cm in FIG. b^-1And 800cm^-1There is a relatively clear absorption peak for Si-C, indicating that the silicon-modified polyether was prepared from the polyether in this example.

Preparation of penetrant of this example:

adding the silicon modified polyether, the fatty alcohol-polyoxyethylene ether sulfate and the alkyl diphenyl ether sulfonate into a reaction kettle according to the formula ratio, stirring and mixing for 30min at normal pressure and room temperature, adding the balance of deionized water, continuing stirring and mixing for 30min, and adjusting the pH value to 7 by using NaOH to obtain the modified polyether.

Example 2

The formulation of each raw material component of the penetrant of this example is shown in table 1. Wherein the alkyl diphenyl ether sulfonate is sodium dodecyl diphenyl ether sulfonate; the fatty alcohol polyoxyethylene sulfate is isomeric tridecanol polyoxyethylene ether sulfate (EO number is 4);

preparation of silicon-modified polyether:

(1) preparation of polyether: 100 parts of isooctanol (6-methyl-1-heptanol) and KOH (the dosage of which is 0.2 percent of the weight of the isooctanol) are added into a pressure reaction kettle, the air in the kettle is replaced by nitrogen for 3 times, the temperature is raised to 110 ℃, and the dehydration is carried out for 30min under the vacuum degree environment below-0.09 MPa. Heating to 120 ℃, slowly dripping ethylene oxide (the molar ratio of the ethylene oxide to the isooctyl alcohol is 3: 1), carrying out ring-opening polymerization reaction under the conditions that the pressure is 0.25MPa and the temperature is 130 ℃, and curing for 30min after the dripping of the ethylene oxide is finished to obtain polyether; the general structural formula is shown as follows:

wherein R-O-is a dehydrogenated part of 6-methyl-1-heptanol, m is 3, and n is 0;

the hydroxyl value [ I (OH) (mg/g) ] of the synthesized polyether is determined according to the method of GB/T7383-2007, and the molecular weight of the polyether is calculated out by using the formula (1) (56.1X 1000)/I (OH).

(2) Adding 100 parts of polyether and sodium methoxide prepared in the step (1) into a pressure reaction kettle, introducing nitrogen, vacuumizing and replacing for 3 times, and mixing and reacting to obtain a mixture; wherein the reaction temperature is 115 ℃, the pressure is-0.095 MPa, and the reaction time is 6 h; the feeding molar ratio of sodium methoxide to polyether is 1.15: 1;

(3) cooling the mixture obtained in the step (2) to 60 ℃, and then dropwise adding 1-chloroethyltrimethylsilane (with the structural general formula of Si (CH)₃)₃-CHClCH₃) Carrying out mixing reaction to obtain a silicon modified polyether crude product; wherein the reaction temperature is 85 ℃, the pressure is 0.15MPa, and the reaction time is 5.5 h; the feeding molar ratio of the 1-chloroethyltrimethylsilane to the polyether is 1.15: 1;

(4) cooling the crude silicon modified polyether to 70 ℃, adding 85 wt% of phosphoric acid to neutralize until the pH value is 4.5, adding 1.5 wt% of adsorbent magnesium silicate (the percentage is the percentage of the adsorbent in the total weight of the crude silicon modified polyether) to adsorb, then carrying out reduced pressure distillation dehydration, and filtering to obtain refined silicon modified polyether, wherein the number average molecular weight is 363g/mol, and the structural general formula is as follows:

wherein R-O-is the dehydrogenation part of isooctyl alcohol (6-methyl-1-heptanol), and R' ism＝3，n＝0。

Preparation of penetrant of this example:

adding the silicon modified polyether, the fatty alcohol-polyoxyethylene ether sulfate and the alkyl diphenyl ether sulfonate into a reaction kettle according to the formula ratio, stirring and mixing for 20min at normal pressure and room temperature, adding the balance of deionized water, continuously stirring and mixing for 40min, and adjusting the pH value to 8 by using NaOH to obtain the modified polyether.

Example 3

The formulation of each raw material component of the penetrant of this example is shown in table 1. Wherein the alkyl diphenyl ether sulfonate is sodium decyl diphenyl ether sulfonate; fatty alcohol polyoxyethylene sulfate C_12-14Alcohol polyoxyethylene ether sulfate (EO number 3);

preparation of silicon-modified polyether:

(1) preparation of polyether: in a pressure reactor, 100 parts of isomeric tridecanol (EXXAL) are added^TM13) And KOH (the dosage of which is 0.3 percent of the weight of the isomeric tridecanol), replacing the air in the kettle with nitrogen for 3 times, heating to 110 ℃, and dehydrating for 30min under the vacuum degree environment of below-0.09 MPa. Heating to 120 ℃, slowly dropwise adding ethylene oxide (the molar ratio of the ethylene oxide to the isomeric tridecanol is 10: 1), carrying out ring-opening polymerization reaction under the conditions that the pressure is 0.35MPa and the temperature is 130 ℃, and after dropwise adding, carrying out curing reaction for 30 min; slowly dripping propylene oxide (the mol ratio of the propylene oxide to the isomeric tridecanol is 3: 1), carrying out ring-opening polymerization reaction under the conditions that the pressure is 0.35MPa and the temperature is 130 ℃, and curing for 30min after the dripping of the propylene oxide is finished to obtain polyether; the general structural formula is shown as follows:

wherein R-O-is isomeric tridecanol (EXXAL)^TM13) And (3) removing hydrogen, wherein m is 10 and n is 3.

The hydroxyl value [ I (OH) (mg/g) ] of the synthesized polyether was determined according to the method of GB/T7383-2007 by using the formula (1): (56.1X 1000)/I (OH), the molecular weight of the polyether was deduced to be 814 g/mol.

(2) Adding 100 parts of polyether and potassium methoxide prepared in the step (1) into a pressure reaction kettle, introducing nitrogen, vacuumizing and replacing for 3 times, and mixing and reacting to obtain a mixture; wherein the reaction temperature is 100 ℃, the pressure is-0.095 MPa (under the vacuum condition, methanol generated by the reaction can be removed), and the reaction time is 8 h; the feeding molar ratio of the potassium methoxide to the polyether is 1.3;

(3) cooling the mixture obtained in the step (2) to 60 ℃, and then dropwise adding chloromethyl trimethylsilane (structural general formula Si (CH)₃)₃-CH₂-Cl) to carry out mixing reaction to obtain a silicon modified polyether crude product; wherein the reaction temperature is 100 ℃, the pressure is 0.15MPa, and the reaction time is 4 h; the feeding molar ratio of chloromethyl trimethylsilane to polyether is 1.1: 1;

(4) cooling the crude silicon modified polyether to 65 ℃, adding 85 wt% of phosphoric acid to neutralize until the pH value is 5, adding 3 wt% of adsorbent magnesium silicate (the percentage is the percentage of the adsorbent in the total weight of the crude silicon modified polyether) to adsorb, then distilling under reduced pressure to dehydrate, and filtering to obtain refined silicon modified polyether with the number average molecular weight of 900 g/mol. The structural general formula is as follows:

wherein R-O-is isomeric tridecanol (EXXAL)^TM13) A dehydrogenated moiety, R' being-CH₂-，m＝10，n＝3。

Preparation of penetrant of this example:

adding the silicon modified polyether, the fatty alcohol-polyoxyethylene ether sulfate and the alkyl diphenyl ether sulfonate into a reaction kettle according to the formula ratio, stirring and mixing for 30min at normal pressure and room temperature, then adding the balance of deionized water, continuously stirring and mixing for 40min, and adjusting the pH value to 6 by using NaOH to obtain the water-soluble silicon dioxide.

Example 4

The formulation of each raw material component of the penetrant of this example is shown in table 1. Wherein the alkyl diphenyl ether sulfonate is sodium hexadecyl diphenyl ether sulfonate; the fatty alcohol polyoxyethylene sulfate is isooctanol polyoxyethylene ether sulfate (EO number is 3);

preparation of silicon-modified polyether:

(1) preparation of polyether: in a pressure reactor, 100 parts of isomeric decaol (EXXAL) are added^TM10) And KOCH₃(the dosage of the catalyst is 0.3 percent of the weight of isomeric dodecyl alcohol), replacing the air in the kettle with nitrogen for 3 times, heating to 110 ℃, and dehydrating for 30min under the vacuum degree environment of-0.09 MPa or below. Heating to 120 ℃, slowly dripping ethylene oxide (the molar ratio of the ethylene oxide to isomeric dodecyl alcohol is 7: 1), carrying out ring-opening polymerization reaction under the conditions that the pressure is 0.3MPa and the temperature is 150 ℃, and curing for 30min after dripping the ethylene oxide to obtain polyether; the general structural formula is shown as follows:

wherein R-O-is isomeric decaol (EXXAL)^TM10) And (3) a dehydrogenized part, wherein m is 7 and n is 0.

The hydroxyl value [ I (OH) (mg/g) ] of the synthesized polyether was determined according to the method of GB/T7383-2007 by using the formula (1): (56.1X 1000)/I (OH), the molecular weight of the polyether was deduced to be 466 g/mol.

(2) Adding 100 parts of polyether and sodium methoxide prepared in the step (1) into a pressure reaction kettle, introducing nitrogen, vacuumizing and replacing for 3 times, and mixing and reacting to obtain a mixture; wherein the reaction temperature is 110 ℃, the pressure is-0.09 MPa (methanol generated by the reaction can be removed under the vacuum condition), and the reaction time is 6 h; the feeding molar ratio of sodium methoxide to polyether is 1.2;

(3) cooling the mixture obtained in the step (2) to 45 ℃, and then dropwise adding gamma-chloropropyltrimethylsilane (with a structural general formula of Si (CH)₃)₃-CH₂CH₂CH₂-Cl) to carry out mixing reaction to obtain a silicon modified polyether crude product; wherein the reaction temperature is 90 ℃, the pressure is 0.2MPa, and the reaction time is 5 h; the feeding molar ratio of the gamma-chloropropyltrimethylsilane to the polyether is 1.1: 1;

(4) cooling the crude silicon modified polyether product to 80 ℃, adding 85 wt% of phosphoric acid to neutralize until the pH value is 5.0, adding 2 wt% of adsorbent magnesium silicate (the percentage is the percentage of the adsorbent in the total weight of the crude product) to adsorb, then distilling under reduced pressure to dehydrate, and filtering to obtain refined silicon modified polyether, wherein the number average molecular weight is 580g/mol, and the structural general formula is as follows:

wherein R-O-is isomeric decaol (EXXAL)^TM10) A dehydrogenated moiety, R' being-CH₂CH₂CH₂-，m＝7，n＝0。

Preparation of penetrant of this example:

adding the silicon modified polyether, the fatty alcohol-polyoxyethylene ether sulfate and the alkyl diphenyl ether sulfonate into a reaction kettle according to the formula ratio, stirring and mixing for 40min at normal pressure and room temperature, adding the balance of deionized water, continuously stirring and mixing for 20min, and adjusting the pH value to 7 by using NaOH to obtain the modified polyether.

Example 5

In this example, the other components and preparation methods of the penetrant are the same as those of example 1, except that the preparation method of the silicon-modified polyether is different.

Preparing silicon modified polyether:

(1) preparation of polyether: in a pressure reactor, 100 parts of isooctanol (EXXAL) are added^TM8) And NaOH (the dosage of which is 0.15 percent of the weight of the isooctyl alcohol), replacing the air in the kettle with nitrogen for 3 times, heating to 110 ℃, and dehydrating for 30min under the vacuum degree environment of below-0.09 MPa. Heating to 120 ℃, slowly dripping ethylene oxide (the molar ratio of the ethylene oxide to the isooctyl alcohol is 5: 1), carrying out ring-opening polymerization reaction under the conditions that the pressure is 0.2MPa and the temperature is 135 ℃, and curing for 30min after dripping the ethylene oxide to obtain polyether; the general structural formula is shown as follows:

wherein R-O-is isooctanol (EXXAL)^TM8) And (3) a dehydrogenized part, wherein m is 5 and n is 0.

The hydroxyl value [ I (OH) (mg/g) ] of the synthesized polyether was determined according to the method of GB/T7383-2007 by using the formula (1): (56.1X 1000)/I (OH), the molecular weight of the polyether was estimated to be 350 g/mol.

(2) Adding 100 parts of polyether and sodium methoxide prepared in the step (1) into a pressure reaction kettle, introducing nitrogen, vacuumizing and replacing for 3 times, and mixing and reacting to obtain a mixture; wherein the reaction temperature is 120 ℃, the pressure is-0.09 MPa (methanol generated by the reaction can be removed under the vacuum condition), and the reaction time is 5 h; the feeding molar ratio of sodium methoxide to polyether is 1: 1;

(3) cooling the mixture obtained in the step (2) to 50 ℃, and then dropwise adding chloromethyl trimethylsilane (structural general formula Si (CH)₃)₃-CH₂-Cl) to carry out mixing reaction to obtain a silicon modified polyether crude product; wherein the reaction temperature is 80 ℃, the pressure is 0.1MPa, and the reaction time is 6 h; the feeding molar ratio of chloromethyl trimethylsilane to polyether is 1.2: 1;

(4) cooling the crude silicon modified polyether to 60 ℃, adding 85 wt% of phosphoric acid to neutralize until the pH value is 4.0, adding 1 wt% of adsorbent magnesium silicate (the percentage is the percentage of the adsorbent in the total weight of the crude silicon modified polyether), adsorbing, then distilling under reduced pressure to dehydrate, and filtering to obtain the silicon modified polyether, wherein the number average molecular weight of the silicon modified polyether is 436g/mol, and the structural general formula of the silicon modified polyether is shown as follows:

wherein R-O-is isooctanol (EXXAL)^TM8) A dehydrogenated moiety, R' being-CH₂-，m＝5，n＝0。

Example 6

Preparing silicon modified polyether:

(1) preparation of polyether: in a pressure reaction kettle, 100 parts of isooctanol (6-methyl-1-heptanol) and NaOCH are added₃(the dosage of the isooctanol is 0.25 percent of the weight of the isooctanol), replacing the air in the kettle with nitrogen for 3 times, heating to 110 ℃, and dehydrating for 30mi under the vacuum degree environment of less than-0.09 MPan is the same as the formula (I). Heating to 120 ℃, slowly dripping ethylene oxide (the molar ratio of the ethylene oxide to the isooctyl alcohol is 10: 1), carrying out ring-opening polymerization reaction under the conditions that the pressure is 0.3MPa and the temperature is 135 ℃, and curing for 30min after dripping the ethylene oxide; slowly dripping propylene oxide (the molar ratio of the propylene oxide to the isooctyl alcohol is 2: 1), carrying out ring-opening polymerization reaction under the conditions that the pressure is 0.3MPa and the temperature is 135 ℃, and curing reaction for 30min after the dripping of the propylene oxide is finished to obtain polyether; the general structural formula is shown as follows:

wherein R-O-is the dehydrogenation part of isooctyl alcohol (6-methyl-1-heptanol), m is 10, and n is 2.

The hydroxyl value [ I (OH) (mg/g) ] of the synthesized polyether was determined according to the method of GB/T7383-2007 by using the formula (1): (56.1X 1000)/I (OH), the molecular weight of the polyether was calculated to be 686 g/mol.

(2) Adding 100 parts of polyether and potassium methoxide prepared in the step (1) into a pressure reaction kettle, introducing nitrogen, vacuumizing and replacing for 3 times, and mixing and reacting to obtain a mixture; wherein the reaction temperature is 110 ℃, the pressure is-0.095 MPa (under the vacuum condition, methanol generated by the reaction can be removed), and the reaction time is 6 h; the feeding molar ratio of the potassium methoxide to the polyether is 1.15;

(3) cooling the mixture obtained in the step (2) to 50 ℃, and then dropwise adding chlorphenyl trimethylsilane (structural general formula)) Carrying out mixing reaction to obtain a silicon modified polyether crude product; wherein the reaction temperature is 110 ℃, the pressure is 0.2MPa, and the reaction time is 5 h; the feeding molar ratio of the chlorphenyl trimethylsilane to the polyether is 1.1: 1;

(4) cooling the crude silicon modified polyether to 70 ℃, adding 85 wt% of phosphoric acid to neutralize until the pH value is 4.5, adding 2 wt% of adsorbent magnesium silicate (the percentage is the percentage of the adsorbent in the total weight of the crude silicon modified polyether) to adsorb, then distilling under reduced pressure to dehydrate, and filtering to obtain refined silicon modified polyether, wherein the number average molecular weight of the refined silicon modified polyether is 834g/mol, and the structural general formula is as follows:

wherein R-O-is a dehydrogenation part of isooctanol (6-methyl-1-heptanol), and R' is a p-phenyl group.m＝10，n＝2。

Example 7

Preparing silicon modified polyether:

(1) preparation of polyether: in a pressure reactor, 100 parts of isomeric decaol (EXXAL) are added^TM10) And KOCH₃(the dosage of the catalyst is 0.4 percent of the weight of isomeric dodecyl alcohol), replacing the air in the kettle with nitrogen for 3 times, heating to 110 ℃, and dehydrating for 30min under the vacuum degree environment of-0.09 MPa or below. Heating to 120 ℃, slowly dripping ethylene oxide (the molar ratio of the ethylene oxide to isomeric dodecyl alcohol is 5: 1), carrying out ring-opening polymerization reaction under the conditions that the pressure is 0.3MPa and the temperature is 145 ℃, and curing for 30min after dripping the ethylene oxide to obtain polyether; the general structural formula is shown as follows:

wherein R-O-is isomeric decaol (EXXAL)^TM10) And (3) a dehydrogenized part, wherein m is 5 and n is 0.

The hydroxyl value [ I (OH) (mg/g) ] of the synthesized polyether was determined according to the method of GB/T7383-2007 by using the formula (1): (56.1X 1000)/I (OH), the molecular weight of the polyether was deduced to be 378 g/mol.

(2) Adding 100 parts of polyether and potassium methoxide prepared in the step (1) into a pressure reaction kettle, introducing nitrogen, vacuumizing and replacing for 3 times, and mixing and reacting to obtain a mixture; wherein the reaction temperature is 105 ℃, the pressure is-0.095 MPa (under the vacuum condition, methanol generated by the reaction can be removed), and the reaction time is 7 h; the feeding molar ratio of the potassium methoxide to the polyether is 1.25;

(3) cooling the mixture obtained in the step (2) to 60 ℃, and then dropwise adding 2-chlorobenzyltrimethylsilane (with a general formula structure as shown in the specification)) Carrying out mixing reaction to obtain a silicon modified polyether crude product; wherein the reaction temperature is 95 ℃, the pressure is 0.2MPa, and the reaction time is 4.5 h; the feeding molar ratio of the 2-chlorobenzyltrimethylsilane to the polyether is 1.05: 1;

(4) cooling the crude silicon modified polyether product to 75 ℃, adding 85 wt% of phosphoric acid to neutralize until the pH value is 4.5, adding 2.5 wt% of adsorbent magnesium silicate (the percentage is the percentage of the adsorbent in the total weight of the crude product) to adsorb, then carrying out reduced pressure distillation dehydration, and filtering to obtain refined silicon modified polyether, wherein the number average molecular weight of the refined silicon modified polyether is 512g/mol, and the structural general formula is as follows:

wherein R-O-is isomeric decaol (EXXAL)^TM10) A dehydrogenizing moiety, R' ism＝5，n＝0。

Example 8

Preparing silicon modified polyether:

(1) preparation of polyether: in a pressure reactor, 100 parts of isomeric tridecanol (EXXAL) are added^TM13) And KOCH₃(the dosage of the water solution is 0.35 percent of the weight of the isomeric tridecanol), replacing the air in the kettle with nitrogen for 3 times, heating to 110 ℃, and dehydrating for 30min under the vacuum degree environment of-0.09 MPa or less. Then heating to 120 ℃, and slowly dripping ethylene oxide (of ethylene oxide and isomeric tridecanol)The molar ratio is 7: 1) carrying out ring-opening polymerization reaction under the conditions that the pressure is 0.25MPa and the temperature is 140 ℃, and carrying out curing reaction for 30min after dropping ethylene oxide to obtain polyether; the general structural formula is shown as follows:

wherein R-O-is isomeric tridecanol (EXXAL)^TM13) And (3) removing hydrogen, wherein m is 7 and n is 0.

The hydroxyl value [ I (OH) (mg/g) ] of the synthesized polyether was determined according to the method of GB/T7383-2007 by using the formula (1): (56.1X 1000)/I (OH), the molecular weight of the polyether was calculated to be 508 g/mol.

(2) Adding 100 parts of random polyether prepared in the step (1) and potassium methoxide into a pressure reaction kettle, introducing nitrogen, vacuumizing and replacing for 3 times, and mixing and reacting to obtain a mixture; wherein the reaction temperature is 80 ℃, the pressure is-0.095 MPa (under the vacuum condition, methanol generated by the reaction can be removed), and the reaction time is 2 h; the feeding molar ratio of the potassium methoxide to the polyether is 1.5;

(3) cooling the mixture obtained in the step (2) to 40 ℃, and then dropwise adding chloromethyl trimethylsilane (structural general formula Si (CH)₃)₃-CH₂-Cl) to carry out mixing reaction to obtain a silicon modified polyether crude product; wherein the reaction temperature is 100 ℃, the pressure is 0.5MPa, and the reaction time is 5 h; the feeding molar ratio of chloromethyl trimethylsilane to polyether is 1.1: 1;

(4) cooling the crude silicon modified polyether to 70 ℃, adding 85 wt% of phosphoric acid to neutralize until the pH value is 5.0, adding 2 wt% of adsorbent magnesium silicate (the percentage is the percentage of the adsorbent in the total weight of the crude silicon modified polyether), adsorbing, then distilling under reduced pressure to dehydrate, and filtering to obtain refined silicon modified polyether, wherein the number average molecular weight of the refined silicon modified polyether is 594g/mol, and the structural general formula is as follows:

wherein R-O-is isomeric tridecanol (EXXAL)^TM13) Dehydrogenation sectionR' is-CH₂-，m＝7，n＝0。

Comparative example 1

The formulation of each raw material component of the penetrant of this comparative example is shown in table 1. Wherein the alkyl diphenyl ether sulfonate is sodium dodecyl diphenyl ether sulfonate; the fatty alcohol polyoxyethylene sulfate is isomeric tridecanol polyoxyethylene ether sulfate (EO number is 4);

the raw material silicon-modified polyether of this comparative example was the same as in example 2.

Preparation of penetrant of this comparative example:

Comparative example 2

TABLE 2

The proportions of the respective raw material components of the penetrant of this comparative example are shown in table 2. In this comparative example, isooctanol polyoxyethylene ether (3EO number) was the penetrating agent JFC conventionally used in the art, fatty alcohol polyoxyethylene sulfate was isomeric tridecanol polyoxyethylene ether sulfate (EO number 4), and alkyl diphenyl ether sulfonate was sodium dodecyl diphenyl ether sulfonate.

Preparation of penetrant of this comparative example:

adding isooctanol polyoxyethylene ether, fatty alcohol polyoxyethylene ether sulfate and alkyl diphenyl ether sulfonate into a reaction kettle according to a formula ratio, stirring and mixing for 20min at normal pressure and room temperature, adding the balance of deionized water, continuously stirring and mixing for 40min, and adjusting the pH value to 8 by using NaOH to obtain the composite material.

Effects of the embodiment

The penetrant prepared in the embodiments 1-4 is colorless or light yellow transparent liquid at 25 ℃, the pH value is 6-8, and the solid content is 40-60%.

The performance of the penetrants prepared in examples 1-4 is compared with that of comparative examples 1-2, and the results are shown in tables 3-6:

TABLE 3

Table 3 shows the alkali-resistant permeability data of the mercerizing penetrants obtained in examples 1-4 and the penetrants obtained in comparative examples 1-2. As shown in Table 3, the mercerizing penetrating agent of the invention has better penetrating power, while the adding amount of the silicon modified polyether in the comparative example 1 is less than the limited range of the invention, and the ideal penetrating effect can not be achieved. After the alkali-resistant permeability is prepared into a sample by using an alkali solution with a certain concentration, the settlement time of the standard canvas in the test solution is determined by using a canvas settlement method according to GB/T11983-2008, and the average value of the settlement time of 5 parallel experiments is taken as the permeability. The shorter the permeation time, the stronger the permeation force. The concentration of the test solution is 5 g/L.

In addition, the alkali-resistant permeability of the penetrants obtained in examples 5-8 is the same as that of the penetrant in example 1.

TABLE 4

Table 4 shows the alkali resistance stability data of the mercerizing penetrants obtained in examples 1-4 and the penetrants obtained in comparative examples 1-2. As can be seen from Table 4, the alkali resistance of the mercerizing penetrant obtained in examples 1-4 reaches 300g/L, and meets the requirements of mercerizing process of cotton and linen fabrics. After a sample is prepared by using an alkali solution with a certain concentration, the appearance state of the solution is observed, the solution is not layered, no aggregate or oily matter floats, the alkali resistance stability is good, and otherwise, the alkali resistance stability is poor. The solution is clear or light blue and transparent, indicating good alkali resistance.

In addition, the alkaline stability of the penetrants obtained in examples 5 to 8 is the same as that of the penetrant of example 1.

TABLE 5

Table 5 shows the foaming performance data of the mercerizing penetrants obtained in examples 1-4 and the penetrants obtained in comparative examples 1-2. As can be seen from Table 5, the mercerizing penetrant of the present invention has excellent low foaming property; in contrast, in comparative example 1, the addition amount of the silicon-modified polyether penetrant is less than the limited range of the present invention, and the foam inhibition effect is general. In comparative example 2, the JFC penetrant conventionally used in the art was used instead of the silicon-modified penetrant used in the present invention, and as can be seen from table 5, comparative example 2 is very poor in low foaming property and is not suitable as a mercerizing penetrant. The method for measuring the foaming performance comprises the following steps: at 25 ℃, 0.3g of a sample to be tested is placed in a 100mL measuring cylinder with a plug, and water is added to dilute the sample to 30mL so as to reach the specified experimental concentration. After the plug is filled, the foaming volume (total volume of solution and foam) is recorded after the plug is vigorously shaken for 10 times and is kept stand for 30s, and the average value of the foaming volume of 3 parallel experiments is taken as the foaming performance index. The smaller the foaming volume, the poorer the foaming power of this variety and therefore the better the low foaming properties.

The foaming performance of the penetrants obtained in examples 5 to 8 was the same as that of the penetrant of example 1.

TABLE 6

Table 6 shows mercerization effect data of the mercerization penetrants obtained in examples 1-4 and the penetrants obtained in comparative examples 1-2. From table 6, it can be seen that the mercerizing penetrant of the present invention has the effect of significantly improving the mercerizing effect. Wherein, the mercerizing finish is as follows: the method comprises the steps of tightly stretching an all-cotton wet fabric (which is not dried after a desizing process and has a liquid carrying rate of 80%) on a tension frame, soaking the fabric in a 280g/L NaOH solution, wherein the temperature of an alkali solution is 25 ℃, the concentration of a mercerizing penetrating agent is 5g/L, and the mercerizing solution is soaked, the liquid binding rate is 110%, washing with hot water after mercerizing, washing with cold water again to be neutral, and airing. The mercerizing effect is tested as follows: the barium value method is that mercerized cotton and non-mercerized cotton are respectively immersed in barium hydroxide solution for a certain time, then the ratio of barium hydroxide absorbed by the mercerized sample and the non-mercerized sample is calculated, the obtained numerical value is the barium value, and the higher the barium value is, the better the mercerization effect of the fabric is.

In addition, the mercerizing effect of the penetrants obtained in examples 5 to 8 is the same as that of the penetrant in example 1.

As can be seen from the above effect examples, example 2 of the present invention is superior to comparative example 2 in low foaming property and mercerization effect on the premise of ensuring the consistency of penetration property and alkali resistance (as shown in data in tables 5 and 6).

Claims

1. The mercerizing penetrating agent is characterized by consisting of the following components: 20-30 wt% of silicon modified polyether, 10-20 wt% of fatty alcohol-polyoxyethylene ether sulfate, 10-20 wt% of alkyl diphenyl ether sulfonate and the balance of water;

the number average molecular weight of the silicon modified polyether is 200-2000 g/mol, and the structural general formula is as follows:

2. The mercerizing penetrant of claim 1, wherein the mercerizing penetrant is free of elemental phosphorus and/or alkylphenol ethoxylates;

the number average molecular weight of the silicon modified polyether is 363-900 g/mol;

the R is straight chain or branched chain C₈～C₁₅Alkyl groups of (a);

said R' is "straight or branched C₁～C₆Alkylene of "or C₆～C₇The sub-aromatic hydrocarbon of (a); m is an integer of 3-15; and/or n is an integer of 0-10.

3. The mercerizing penetrant of claim 2, wherein the silicon-modified polyether has a number average molecular weight of 436-834 g/mol;

r is C of a branched chain₈～C₁₅Alkyl groups of (a);

said R' is "straight or branched C₁～C₃An alkylene group of,Or(ii) a M is an integer of 5-10; and/or n is 2.

4. The mercerizing penetrant of claim 3 wherein the silicon-modified polyether has a number average molecular weight of 512g/mol, 580g/mol, 594g/mol or 744 g/mol;

r is C of a branched chain₈Alkyl, branched C of₁₀Alkyl or branched C of₁₃Alkyl groups of (a); c of said branched chain₈The alkyl group of (A) is 6-methyl-1-heptanol or EXXAL^TM8 dehydroxylated moieties; c of said branched chain₁₀Alkyl of (A) is EXXAL^TM10 a dehydroxylated moiety; c of said branched chain₁₃Alkyl of (A) is EXXAL^TM13 a dehydroxylated moiety;

the straight chain or branched C₁～C₃Alkylene of (a) is-CH₂-、or-CH₂CH₂CH₂-; and m is 7 or 9.

5. The mercerizing penetrant of claim 1 wherein the silicon-modified polyether is prepared by the steps of: (1) under an oxygen-free atmosphere, mixing polyether and organic base for reaction to obtain a mixture; wherein the reaction temperature is 80-140 ℃; the organic base is sodium methoxide and/or potassium methoxide; the feeding molar ratio of the organic base to the polyether is (1.0-1.5): 1; the structural general formula of the polyether is as follows:

(2) cooling the mixture obtained in the step (1), and mixing the mixture with halogenated alkyl trimethyl silane for reaction to obtain the silicon modified polyether; wherein the reaction temperature is 60-120 ℃; the feeding molar ratio of the halogenated alkyl trimethylsilane to the polyether is (1.0-1.4): 1; the structural general formula of the halogenated alkyl trimethylsilane is shown as follows: si (CH)₃)₃-R’-X；

6. The mercerizing penetrant of claim 5 wherein in step (1), the oxygen-free atmosphere is nitrogen and/or argon;

in the step (1), the reaction temperature is 100-120 ℃;

in the step (1), the reaction time is 2-10 h;

in the step (1), the pressure of the reaction is-0.08 to-0.095 MPa;

in the step (1), the feeding molar ratio of the organic base to the polyether is 1.15-1.3: 1;

and/or, in step (1), the polyether is prepared by the following steps: under an oxygen-free atmosphere, firstly dripping ethylene oxide into a mixture containing initiator alcohol and a catalyst, carrying out a first ring-opening polymerization reaction and a first curing reaction, then dripping propylene oxide, and carrying out a second ring-opening polymerization reaction and a second curing reaction to obtain the catalyst; wherein the initiator alcohol is a linear or branched C6-C18 alkyl alcohol, and the molar ratio of the ethylene oxide to the initiator alcohol is (1-20): 1, the molar ratio of the propylene oxide to the initiator alcohol is (0-20): 1.

7. The mercerizing penetrating agent according to claim 5, wherein in the step (1), when the polyether and the organic base are mixed and reacted, the reaction temperature is 105-115 ℃;

in the step (1), when polyether and organic base are mixed and reacted, the reaction time is 5-8 h;

in the step (1), when polyether and organic base are mixed and reacted, the reaction pressure is-0.09 MPa;

in the step (1), the feeding molar ratio of the organic base to the polyether is 1.25: 1.

8. the mercerizing penetrant of claim 5 wherein in step (1), when the polyether and the organic base are mixed and reacted, the reaction temperature is 110 ℃;

in the step (1), when the polyether and the organic base are mixed and reacted, the reaction time is 6-7 h.

9. The mercerizing penetrant of claim 6 wherein in the polyether manufacturing process, the oxygen-free atmosphere is nitrogen and/or argon;

in the preparation method of the polyether, the catalyst and the initiator alcohol are pretreated before the ring-opening polymerization reaction is carried out; the pretreatment is carried out according to the following steps: dehydrating the catalyst and the initiator alcohol for 25-35 min at the temperature of 105-115 ℃ and the pressure of-0.095-0.085 MPa in an oxygen-free atmosphere;

in the preparation method of the polyether, the catalyst is KOH, NaOH or KOCH₃And NaOCH₃One or more of;

in the preparation method of the polyether, the dosage of the catalyst is 0.05-1 wt% of that of the initiator alcohol;

in the preparation method of the polyether, the initiator alcohol is linear chain or branched chain C₈～C₁₅Alkyl alcohol of (2)；

In the preparation method of the polyether, the temperature of the first ring-opening polymerization reaction and the second ring-opening polymerization reaction is independently 120-160 ℃; the pressure of the first ring-opening polymerization reaction and the pressure of the second ring-opening polymerization reaction are independently 0.05-0.35 MPa; the time of the first curing reaction and the second curing reaction is 25-35 min independently;

in the preparation method of the polyether, the molar ratio of the ethylene oxide to the initiator alcohol is (3-15): 1;

and/or in the preparation method of the polyether, the molar ratio of the propylene oxide to the initiator alcohol is (2-10): 1.

10. The mercerizing penetrant of claim 9 wherein said pretreatment is performed by the steps of: dehydrating the catalyst and the initiator alcohol for 30min at the temperature of 110 ℃ and the pressure of-0.09 MPa in an oxygen-free atmosphere;

in the preparation method of the polyether, the dosage of the catalyst is 0.15-0.4 wt% of that of the initiator alcohol;

in the preparation method of the polyether, the initiator alcohol is branched C₈～C₁₅Alkyl alcohol of (1);

in the preparation method of the polyether, the temperature of the first ring-opening polymerization reaction and the second ring-opening polymerization reaction is 130-150 ℃; the pressure of the first ring-opening polymerization reaction and the pressure of the second ring-opening polymerization reaction are independently 0.2-0.3 MPa; the time of the first curing reaction and the second curing reaction is independently 30 min;

in the preparation method of the polyether, the molar ratio of the ethylene oxide to the initiator alcohol is (5-10): 1.

11. the mercerizing penetrant of claim 10 wherein in the polyether manufacturing process, the catalyst is used in an amount that is 0.2 wt%, 0.25 wt%, 0.3 wt%, or 0.35 wt% of the amount of starter alcohol;

the above-mentionedIn the preparation method of polyether, the initiator alcohol is branched C₈Alkyl alcohol, branched C₁₀Alkyl alcohol or branched C₁₃Alkyl alcohol of (1); wherein, C of the branched chain₈The alkyl alcohol is 6-methyl-1-heptanol or EXXAL^TM8; c of said branch chain₁₀The alkyl alcohol of (A) is EXXAL^TM10; c of said branch chain₁₃The alkyl alcohol of (A) is EXXAL^TM13；

In the preparation method of the polyether, the temperature of the first ring-opening polymerization reaction and the second ring-opening polymerization reaction is 135 ℃, 140 ℃ or 145 ℃ independently; the pressure of the first ring-opening polymerization reaction and the second ring-opening polymerization reaction is independently 0.25 MPa;

in the preparation method of the polyether, the molar ratio of the ethylene oxide to the initiator alcohol is 7: 1 or 9: 1.

12. the mercerizing penetrant of claim 5, wherein in step (2), the temperature after cooling is 40-60 ℃;

in the step (2), the halogenated alkyl trimethylsilane is chloroalkyl trimethylsilane, bromoalkyl trimethylsilane or iodoalkyl trimethylsilane;

in the step (2), the reaction temperature is 80-110 ℃;

in the step (2), the reaction time is 2-8 h;

in the step (2), the pressure of the reaction is 0-0.5 MPa;

and/or in the step (2), the feeding molar ratio of the halogenated alkyl trimethylsilane to the polyether is (1.05-1.2): 1.

13. the mercerizing penetrant of claim 12, wherein in step (2), the temperature after cooling is 45-50 ℃;

in the step (2), the chloroalkyltrimethylsilane is chloromethyltrimethylsilane, 1-chloroethyltrimethylsilane, gamma-chloropropyltrimethylsilane, (2-chlorobenzyl) -trimethylsilane or p-chlorophenyltrimethylsilane;

in the step (2), the reaction temperature is 85-105 ℃;

in the step (2), the reaction time is 4-6 h;

in the step (2), the pressure of the reaction is 0.1-0.2 MPa;

and/or in the step (2), the feeding molar ratio of the halogenated alkyl trimethylsilane to the polyether is (1.1-1.15): 1.

14. the mercerizing penetrant of claim 13 wherein in step (2), the temperature of the reaction is 90 ℃, 95 ℃ or 100 ℃;

in the step (2), the reaction time is 4.5h, 5h or 5.5 h;

in the step (2), the pressure of the reaction is 0.15 MPa.

15. The mercerizing penetrant of claim 5 wherein the mixture after the mixing reaction of step (2) is subjected to a post-treatment operation; the post-treatment is carried out according to the following steps: cooling the mixture obtained after the mixing reaction in the step (2) to 60-80 ℃, adjusting the pH value to 4.0-5.0, adsorbing with an adsorbent, dehydrating, and filtering to obtain the catalyst;

the dosage of the adsorbent is 0.5-5% of the total weight of the mixture after the mixing reaction in the step (2).

16. The mercerizing penetrant of claim 15 wherein the temperature after cooling is 65-75 ℃;

the pH value is 4.5;

the pH value regulator for regulating the pH value is phosphoric acid;

the adsorbent is magnesium silicate;

the dosage of the adsorbent is 1-3% of the total weight of the mixture after the mixing reaction in the step (2).

17. The mercerizing penetrant of claim 16 wherein the cooled temperature is 70 ℃;

the dosage of the adsorbent is 1.5%, 2% or 2.5% of the total weight of the mixture after the mixing reaction in the step (2).

18. The mercerizing penetrating agent according to claim 1, wherein in the fatty alcohol-polyoxyethylene ether sulfate, the number of carbon atoms of fatty alcohol is 8-14; the number of ethylene oxide is 3-4;

the dosage of the fatty alcohol-polyoxyethylene ether sulfate is 15-18 wt%;

the alkyl diphenyl ether sulfonate is sodium alkyl diphenyl ether sulfonate;

in the alkyl diphenyl ether sulfonate, the carbon atom number of the alkyl is 8-16; the dosage of the alkyl diphenyl ether sulfonate is 14-15%;

and/or the water is deionized water.

19. The mercerizing penetrant of claim 18 wherein in the fatty alcohol polyoxyethylene ether sulfate, the number of carbon atoms in the fatty alcohol is 10, 12 or 13;

the alkyl diphenyl ether sulfonate is sodium dodecyl diphenyl ether sulfonate, sodium decyl diphenyl ether sulfonate, sodium octyl diphenyl ether sulfonate or sodium hexadecyl diphenyl ether sulfonate;

in the alkyl diphenyl ether sulfonate, the carbon atom number of the alkyl is 10-12.

20. A method for preparing the mercerizing penetrant according to any one of claims 1 to 19, which comprises the following steps: and (2) uniformly mixing the silicon modified polyether, the fatty alcohol-polyoxyethylene ether sulfate and the alkyl diphenyl ether sulfonate mixture with the water, and then adjusting the pH value to 6-8 to obtain the modified polyether.

21. The method of claim 20, wherein the mixture is prepared by: stirring and mixing for 20-40 min at normal pressure and room temperature;

when the mixture of the silicon modified polyether, the fatty alcohol-polyoxyethylene ether sulfate and the alkyl diphenyl ether sulfonate is mixed with the water, the mixing time is 20-40 min;

and/or the pH is 7.

22. The method of claim 20, wherein the mixture is prepared by: stirring and mixing for 30min at normal pressure and room temperature;

when the mixture of the silicon modified polyether, the fatty alcohol-polyoxyethylene ether sulfate and the alkyl diphenyl ether sulfonate is mixed with the water, the mixing time is 30 min.