CN112064409A

CN112064409A - Composite fatty acid color brightness regulator and preparation method and application thereof

Info

Publication number: CN112064409A
Application number: CN201910501699.2A
Authority: CN
Inventors: 游桥平
Original assignee: GUANGZHOU TENGLONG MATERIAL SC
Current assignee: GUANGZHOU TENGLONG MATERIAL SC
Priority date: 2019-06-11
Filing date: 2019-06-11
Publication date: 2020-12-11

Abstract

The invention relates to a composite fatty acid color brightness regulator and a preparation method and application thereof. The composite fatty acid color brightness regulator comprises a main material; the main material is composed of compound fatty acid sorbitol secondary ester and C₁₂Saturated fatty acid polyoxyethylene (6) ether and C₁₇The saturated fatty acid polyoxyethylene (6) ether is prepared by compounding and crosslinking potassium hydroxide and EDTA disodium salt; wherein the compound fatty acid in the compound fatty acid sorbitol secondary ester is C₁₂Saturated fatty acids and C₁₇A saturated fatty acid. The composite fatty acid color brightness regulator can be used effectivelyThe whiteness of plant fibers such as paper pulp, textile products and the like is improved, the added value is high, the light and color retention is excellent, the color and the brightness of various products treated by the method are in pure natural artistic sense, and the method has no fluorescence value, no radiation, environmental protection, sanitation, low application cost and high cost performance.

Description

Composite fatty acid color brightness regulator and preparation method and application thereof

Technical Field

The invention relates to the technical field of organic synthesis and pulping and papermaking processes, in particular to a composite fatty acid color brightness regulator and a preparation method and application thereof.

Background

With the rapid development of modern construction in our country, the living standard of people is continuously improved, the requirements on various finished paper (or paper products), textiles and dyeing and finishing products produced in the pulping and papermaking industry, the textile industry and the dyeing and finishing industry are higher and higher, meanwhile, the environment-friendly quality is also required to be improved, the energy is saved, the emission is reduced, the environmental pollution is reduced, the natural resources are promoted and improved, and the comprehensive utilization of recycling economy is also required, so that the transformation and the upgrade of the industry are accelerated, and the sustainable and healthy development of the national industry is promoted.

Based on this, various fluorescent whitening agents with negative effects, such as VBL, UBL, VRL, RDL, etc., adopted in the traditional pulping and papermaking industry, textile industry and dyeing and finishing industry, have been unable to meet the needs of market consumption, mainly because of the following reasons: the fluorescence value of the product whitened by the fluorescent whitening agent is too high and reaches 8.0-18.0%; poor light and color retention; hard water intolerance (the whitening effect is lost when the water hardness is more than 300 ppm) and serious water pollution, which is not beneficial to improving the quality of environmental protection, and the like. In addition, the fluorescent component in the fluorescent whitening agent has strong radiation property and carcinogenicity to human body and various organisms, and the radiation dose can reach 4.76 multiplied by 10^-3Rads, such components remaining in the product, inevitably pose a threat to human health.

Disclosure of Invention

Based on the above, there is a need for providing a composite fatty acid color brightness regulator. The composite fatty acid color brightness regulator can effectively improve the whiteness of plant fibers such as paper pulp, textile and the like, has high added value and excellent light and color retention, and various products treated by the composite fatty acid color brightness regulator have pure natural artistic feelings of color and brightness, no fluorescence value, no radiation, environmental protection, sanitation, low application cost and high cost performance.

A composite fatty acid color brightness regulator comprises a main material, butyl stearate, nonylphenol polyoxyethylene (4/10) ether phosphate potassium salt and a dispersing agent; the main material consists of compound fatty acid sorbitol secondary ester and C₁₂Saturated fatty acid polyoxyethylene (6) ether and C₁₇Saturated fatty acid polyoxyethylene (6) ether is crosslinked; wherein the compound fatty acid in the compound fatty acid sorbitol secondary ester is C₁₂Saturated fatty acids and C₁₇A saturated fatty acid; what is needed isThe cross-linking agent adopted for cross-linking is EDTA disodium salt.

In one embodiment, C₁₂The saturated fatty acid is lauric acid.

In one embodiment, C₁₇The saturated fatty acid is stearic acid.

In one embodiment, the complex fatty acid sorbitol secondary ester, C₁₂Saturated fatty acid polyoxyethylene (6) ether, C₁₇The molar ratio of the saturated fatty acid polyoxyethylene (6) ether to the crosslinking agent used for crosslinking is 1.5-2.5: 1.5-2.5: 1.5-2.5: 1.

in one embodiment, the method of crosslinking comprises the steps of: dissolving the cross-linking agent by using aqueous solution of alkali, adding the compound fatty acid sorbitol secondary ester and C under stirring₁₂Saturated fatty acid polyoxyethylene (6) ether and C₁₇And (3) carrying out ester exchange reaction on three materials of saturated fatty acid polyoxyethylene (6) ether.

In one embodiment, the base is potassium hydroxide. The concentration of the potassium hydroxide aqueous solution is 20.0-25.0%.

In one embodiment, the preparation method of the compound fatty acid sorbitol secondary ester comprises the following steps:

subjecting said C to₁₂Saturated fatty acid, C₁₇Mixing saturated fatty acid and sorbitol, and carrying out esterification reaction under the catalysis of a catalyst to obtain the product; said C is₁₂Saturated fatty acid, C₁₇The molar ratio of saturated fatty acid to sorbitol is 0.2-0.4: 0.2-0.4: 1.

in one embodiment, the catalyst is a complex of sulfuric acid and linear alkyl benzene Sulfonic Acid (SAS).

In one embodiment, C₁₂Saturated fatty acid polyoxyethylene (6) ether is prepared from C₁₂Saturated fatty acid and ethylene oxide are polymerized; said C is₁₂The molar ratio of saturated fatty acid to ethylene oxide is 1: 6.

in one embodiment, C₁₇Saturated fatty acid polyoxyethylene (6) ether is prepared from C₁₇Saturated fatty acid and ethylene oxide are polymerized; said C is₁₇The molar ratio of saturated fatty acid to ethylene oxide is 1: 6.

in one embodiment, the polymerization is catalyzed by potassium hydroxide.

In one embodiment, the potassium nonylphenol polyoxyethylene (4/10) ether phosphate is prepared by phosphatizing and salifying nonylphenol polyoxyethylene (4) ether and nonylphenol polyoxyethylene (10) ether; the molar ratio of the nonylphenol polyoxyethylene (4) ether to the nonylphenol polyoxyethylene (10) ether is 0.8-1.2: 0.8-1.2.

In one embodiment, the dispersing agent is compound fatty alcohol polyoxyethylene (6/15) ether sodium sulfonate, which is prepared from secondary octanol polyoxyethylene ether (6) ether and C_12/15The isomerized fatty alcohol polyoxyethylene (15) ether is prepared by sodium sulfite acidification and sodium carbonate neutralization; the secondary octanol polyoxyethylene ether (6) ether and C_12/15The molar ratio of the isomerized fatty alcohol-polyoxyethylene (15) ether is 0.8-1.2: 0.8-1.2.

In one embodiment, the dosage ratio of the sodium carbonate is the secondary octanol polyoxyethylene ether (6) ether and C_12/151.0-3.0% of the total weight of the isomerized fatty alcohol polyoxyethylene (15) ether.

In one embodiment, the composite fatty acid color brightness regulator is prepared from the following raw materials in percentage by weight:

the invention also provides a preparation method of the composite fatty acid color brightness regulator, which comprises the following steps:

obtaining the main material, controlling the temperature to be 70-80 ℃ and the pH value to be 8-8.5, adding the butyl stearate, stirring, adding the potassium nonylphenol polyoxyethylene (4/10) ether phosphate and the composite fatty alcohol polyoxyethylene (6/15) ether sodium sulfonate, maintaining the temperature to be 70-80 ℃ and the pH value to be 8-8.5, reacting for 45-55 hours, and cooling;

and (3) when the temperature is reduced to 35-40 ℃, adding the 27.5% hydrogen peroxide for oxidation reaction until no foam is generated, simultaneously leading out the foam generated in the oxidation reaction process, spraying the foam into ethyl acetate for foam pressing to obtain a treatment solution, and merging the treatment solution into the reaction solution of the oxidation reaction.

The invention also provides application of the composite fatty acid color brightness regulator in papermaking, printing and dyeing, emulsion preparation or coating.

Compared with the prior art, the invention has the following beneficial effects:

the composite fatty acid color brightness regulator is innovatively prepared by compounding and crosslinking raw materials based on saturated fatty acid, and has the following advantages:

(1) the fluorescent whitening agent can replace the existing fluorescent whitening agent, improve the brightness, whiteness and color (hue) of the papermaking plant fibers and the textile fibers, and the finished paper made by the papermaking can present pure natural artistic color, has no fluorescence value, no radiation, environmental protection and sanitation, low application cost and high cost performance;

(2) good puffing and softening functions; the swelling rate can reach 5.0-8.0%, and the softness can reach 5.0mm (clearance test); the surface smoothness of various finished paper and fabric products can be improved, and the paper and fabric products have greasy and smooth feeling;

(3) excellent emulsification, dispersion, permeation and level dyeing effects; can effectively improve the whiteness of paper pulp and fabric products;

(4) excellent anti-pollution, antistatic and anti-redeposition performances, can keep the surfaces of finished paper and fabric products always clean and sanitary conditions, and reduce the erosion of pollutants.

Detailed Description

The compound fatty acid color brightness regulator of the present invention, its preparation method and application are further described in detail with reference to the following specific examples.

Unless otherwise specified, the percentages (%) in the present invention are all by weight.

The embodiment of the invention provides a composite fatty acid color brightness regulator, which comprises a main material and a composite fatSecondary esters of fatty acids sorbitol, C₁₂Saturated fatty acid polyoxyethylene (6) ether and C₁₇The saturated fatty acid polyoxyethylene (6) ether is prepared by carrying out ester exchange, potassium hydroxide and EDTA disodium salt composite crosslinking on three materials; wherein the compound fatty acid in the compound fatty acid sorbitol secondary ester is C₁₂Saturated fatty acids and C₁₇A saturated fatty acid.

The technical exploration and technical conception of the composite fatty acid color brightness regulator are as follows:

first, technical exploration

1.1 one of the exploration bases: research of commodity market industry

If the daily commodities such as daily paper, packaging paper and other special papers, cotton textiles, plastic buttons for clothes and the like contain fluorescence values, the daily commodities have radiation and carcinogenic effects on human bodies, and if the daily commodities are frequently contacted with the commodities, the physical and psychological health and the family happiness of people can be seriously threatened and influenced. Thus, many people in the pulp and paper industry have long recognized the fluorescent whitening agent, but the fluorescent whitening agent is not available at present.

1.2 two search criteria: waste paper raw material is used for replacing primary wood pulp or pulp board

In the early nineties of the last century, certain pulping and papermaking enterprises use reeds as raw materials to produce bleached chemical pulp, but normal production cannot be carried out due to environmental protection problems. The company finds out other approaches for technical innovation, tries to use mixed magazine paper waste paper as a raw material to replace reed or other wood raw materials to prepare bleached chemical pulp and finds out an inventor with a preselected mixed magazine waste paper sample to explain the intention and the strive for meeting the requirements, and the inventor carries out a whiteness analysis test according to the whiteness, the hue index and the corresponding met requirements of the waste paper sample provided by the other side; and the bleached reed chemical pulp was used for comparison. The comparative results are shown in table 1:

TABLE 1 comparison of whiteness and color indexes of bleached reed chemical pulp and mixed magazine waste pulp

The inventor carries out comprehensive analysis simulation according to the comparison result in the table 1 and decides to adopt the flotation deinking process to carry out initial treatment, and the treatment process comprises the following steps: pulping → roughing → dilution → thermal dispersion → flotation → washing → concentration → refining → pulp preparation → to paper making system. From the two steps of deinking flotation and washing, only the product of deinking agent containing the flotation agent and the collecting agent with saponification value of more than 150-200 mgKOH/g has better flotation effect and washing effect, and has better antistatic performance. In the preliminary exploration and treatment of the existing compounds, grafts or derivatives of fatty acids and fatty acid esters (e.g., fatty acid polyoxyethylene ester polymers), the mixed magazine waste pulp has a whiteness value of 83.76%, L of 92.976, a of 0.741, b of 3.64, and a dust degree of 12.0 pieces/m²Although the treatment effect is improved, the effect of imitating wood pulp is not achieved, and further improvement and perfection are needed by the inventor.

1.3 search three: comprehensive comparison of various fatty acids

The inventors have conducted extensive and systematic studies and comparisons of various fatty acids in an all-round manner, and classified the various fatty acids into two major types: namely saturated fatty acids and unsaturated fatty acids. The saturated fatty acids include lauric acid and stearic acid; the unsaturated fatty acids include cottonseed oleic acid, coconut oleic acid, linolenic acid, tea seed oleic acid, soybean oleic acid, rapeseed oleic acid, and the like. The molecular chain of the saturated fatty acid has no C ═ C olefin structure, and the molecular chain of the unsaturated fatty acid has 2-3C ═ C olefin structures; the basic characteristics exhibited during the scientific research and industrial application are shown in table 2:

TABLE 2 comparison of properties of several commonly used saturated and unsaturated fatty acids in scientific research and industrial application

Lauric acid has a refractive index of 1.4267, stearic acid has a refractive index of 1.4299, and palmitic acid has a refractive index of 1.43807. As can be seen from table 2, the iodine value of the saturated fatty acid is much smaller than that of the unsaturated fatty acid (this is the fundamental difference between the two), the density is relatively large, the chemical properties are relatively stable, and the unsaturated fatty acid is resistant to oxidation and not prone to deterioration. On the other hand, saturated fatty acids such as lauric acid, stearic acid and palmitic acid (palmitic acid) all have a refractive index of 1.4267 or more, and unsaturated fatty acids have no reference of refractive index; this is also a fundamental difference between unsaturated and saturated fatty acids. Lauric acid, stearic acid and palmitic acid are industrially used as white solid particles or platelets; the inventor finds that the whitening effect of the whitening agent and peroxide is good, and even under the condition of active products such as fatty acid polyoxyethylene ester and the like generated by ethylene oxide under the catalysis of alkali, the whitening effect can be improved by 2.0-3.0 times; the whitened fiber and the textile product have no fluorescence value, and the appearance of the whitened fiber, finished paper and the textile product is natural artistic color, so that the aim of simulating natural fiber can be achieved. Through a large number of experimental processes, the inventor observes in detail that the waste paper is used for pulping, the whiteness value of the pulp is 88.37%, the L value is 96.396, a is 0.001, and b is 2.81; the effect of bleaching reed chemical pulp has been substantially approached.

1.4 search four bases: solves the problems of whiteness and softness of products in the textile printing and dyeing industry

The textile fiber includes cotton fiber, chemical fiber, blended fiber, etc. These textile fiber materials mostly have an oriented linear or cross-linked linear polymer structure; and the number average polymerization degree is mostly between 5500 and 17000; if a product with a small quantity and a low use cost is required, the effects of no fluorescence, whitening, good light and color retention and excellent flexibility are ensured. Since the fiber stock used in papermaking has whitening, softening and brightness improving effects, it is expected to be equally applicable to textile fibers and textile products.

1.5 subject matter to which the invention is directed

The four exploration bases are integrally searched and summarized, and the approximately solved subject contents are as follows:

for one of the bases: the whiteness value of finished paper, textile fiber and textile products can be effectively improved, and the fluorescence whiteness value F is 0.

For the second criterion: the pulp produced by using waste paper raw materials with various whiteness values of more than 50.0 percent can achieve the effect of simulating pure natural primary wood pulp (after deinking and whitening), and the whiteness values, L, a, b and the like all need to reach corresponding numerical values according to different variety specifications, so that the fluorescence whiteness value F is 0.

For the third criterion: when various fatty acids are researched, the discovery and the verification show that the iodine value is small, the refractive index is high, the oxidation resistance is high, the stability is good, and the real whiteness value can be easily and greatly improved. Saturated fatty acids (such as lauric acid, stearic acid, palmitic acid and the like) and fatty acid polyoxyethylene esters of which F is 0.

According to the fourth aspect, it is desired to increase the whiteness value and softness of the textile fibers, and at the same time, to assist in the sizing of the fabric.

After all, the four bases determine the key points and the convergence points of the subject matter of the present invention, namely how to improve the whiteness (ISO value) and the plant softness of the plant fiber (plant fiber raw materials are mostly adopted for paper making and textile), and ensure that the fluorescence whiteness value F is 0; the color of the bleached artificial natural plant fiber is strived to be achieved.

1.6 technical difficulties

The technical difficulties of the invention are focused on improving the whiteness and the softness of the plant fiber under the condition of no fluorescence by using a single variety and using a small amount (1.0-3.0 Kg/MT); it must also have the color brightness (L, a, b) of the simulated bleached natural raw pulp, which is very difficult under the conditions of pulping, paper making and dyeing and finishing with large amount of hard water. Because the fluorescent component-containing groups or functional groups in the fluorescent whitening agents (VBL, UBL, etc.) can form blue light and yellow light after reacting with-OH, -O-, -ONa, etc. of cellulose molecules in the plant fibers, the color coordinate values are generally a (0.31) and b (0.23). Such chromophoric groups increase the whiteness of plant fibers in a whitening manner, but when the water hardness exceeds 200ppm (in terms of calcium, magnesium and heavy metal ions), there is almost no whitening effect. Therefore, under the conditions of high water hardness and no fluorescence, the method is very difficult to improve the real whiteness of the pulp and the textile fiber, and no existing theoretical basis can be used for reference.

Second, the technical idea

2.1 one of the design bases

The central task and focus of the invention is to improve the whiteness value (ISO value) of the plant fiber, improve the color (a, b value) and the brightness (L value) on the premise of not containing the fluorescence value, and strive to make the plant fiber show pure natural artistic color and luster after the action. A large number of scientific experimental results and production practical experience prove that: the brightness L value of the plant fiber is improved, and the whiteness value of the plant fiber is actually improved; because L is in a proportional relationship with the ISO value; while whiteness is simply the hue of the color (related to the a, b values). In a general situation, people are used to talk about the ISO value and the L value, and it is very unknown that the L value is an optical property, and the ISO value is only a hue index; although they are related, they are different in concept and property. Indeed, the present invention always uses fluorescent whitening agents such as VBL, UBL, VRU, etc. as reference substances, and seeks to synthesize alternatives for other materials in view of their deficiencies and drawbacks. The most prominent defects of products such as VBL, UBL, VRU and the like are as follows: the hardness of the water quality is more than 300ppm/L, the function of whitening plant fibers can not be basically obtained, and the whitening effect on mechanical pulp and chemical mechanical pulp is not really realized; even if the whitening agent has whitening effect on chemical pulp fibers, the whitening agent has poor light and color retention under the irradiation of sunlight or ultraviolet rays. The fluorescent whitening agent has such a drawback that the fluorescent whitening agent is mainly composed of 〡 ethylene sodium 1, 2-bis 〡 4- [ 2-anilino-4- (2-monoethanol-2-amino) -1, 3, 5-triazine-6-imino ] -2-benzenesulfonate or 〡 ethylene 1, 2-bis 〡 4- (2-p-sodium-sulfonanilo-4-diethylamino-1, 3, 5-triazine-6-imino) -2-benzenesulfonate, and the group of amino group and C-N, C ═ N group in the benzene heterocycle have strong external strengthReducing property; and the reactive functional group-SO₃Na，-SO₃H has an oxidizing property, -NH, C-N, C ═ N, and the like, and is combined with — OH, -O-in the cellulose molecule to form a light yellow + light blue ═ white color-emitting group; the whitening effect is visually seen from the surface, but the chromaticity of the white is that of magnesium oxide (MgO) as a reference state; for pulps containing residual lignin, once VBL, O-NH, C-N and C ═ N in VRU undergo coordination reactions with other heavy metal ions, this bluish color scale is not revealed and the whitening function is lost. The inventors found that the fluorescent whitening agent is a mixed color standard value, specifically (0.27, 0.31, 0.33, 0.36, 0.46) by photoelectric induction and fluorescent probe analysis methods. The inventor finds that the fluorescent whitening agent has certain whitening effect on waste paper pulp with light blue, light yellow and pure white through simulation integration of various color scale values, but loses whitening effect if encountering plant fibers polluted by various polychromatic dyes or dispersion media with higher water hardness.

2.2 concept two

According to the general natural law, the bleaching or whitening process of plant fibers such as paper pulp, textile and the like is essentially the oxidation process of the plant fibers; because the removal of melanin and surface dirt (contaminants) from the fibers can only be achieved by means of oxidation. The fluorescent whitening agent also makes active groups or functional groups containing fluorescent components react with-OH, -O-, -ONa and the like of cellulose molecules in the plant fiber raw materials to generate chromophoric groups with blue light through an oxidation-reduction reaction process on the plant fiber raw materials which are whitened by more than 70.0 percent; and the whiteness value of the plant fiber is increased in a whitening manner by the chromophoric groups, but the whiteness is unstable; after the fiber is irradiated by sunlight or ultraviolet rays for 1.0 to 2.0 hours, the surface of the fiber is yellow, the whiteness is reduced to the original whiteness value, the reducibility is strong, and the light and color retention are poor; this reduction is an external reduction. Aiming at the defects of the fluorescent whitening agent, the invention is innovatively inspired by taking the soap washing principle as a concept basis; because the soap has good decontamination and whitening effects on white clothes or white cotton yarn in an objective state, the difference is that more than 80% of main raw materials used in the production process of the soap adopt mixed unsaturated fatty acid, sodium silicate with Baume degree of 460 is added, the amount of the sodium silicate is about 16-18%, nonionic surfactant and the like, but the soap has poor dispersion and permeation effects in a liquid state; the clothes can be washed only by rubbing or rubbing. The biggest difference of the soap for whitening clothes is that the whitening of clean clothes and cotton yarns is realized by multiple actions of washing, decontamination, activation, level dyeing and the like. Although the whitening effect is not obvious, the whitening effect belongs to a net increased whiteness value without blue light; the yellow-resistant paint has the advantages of no yellowing under the irradiation of sunlight or ultraviolet rays, no reduction of whiteness, excellent light and color retention and no reducibility. The whiteness and color of the garments typically washed with soap are: ISO, 80.0-84.0%; l, 93.497-96.145; a, 0.001; b, 1.90-2.21. Clothes and cotton yarns or cotton textiles are purely white mechanical fibers.

2.3 concept rules

The basic principle of the inventive concept is based on two basic conditions:

2.3.1 improving the whiteness of the plant fiber, including various chemical pulp waste paper, chemical mechanical pulp waste paper, cotton textiles and the like in the papermaking raw materials; firstly, the method and the measures of multiple functions of washing, decontamination, decoloration, activation, leveling, infiltration and the like are adopted to achieve the expected whitening effect, and secondly, the numerical range of L, a, b and the like is adjusted. The contents of the whiteness values are preliminarily defined as total whiteness value (. SIGMA ISO), initial whiteness base value (ISO)₀) And net added whiteness value (Δ ISO); the relationship between the three is defined as: sigma ISO ═ ISO₀+△ISO。

2.3.2 Using the third search criterion, the results were compared in an all-round manner and studied more systematically and progressively with the aid of the three types of unsaturated fatty acids and the three types of saturated fatty acids described in Table 2. The research result shows that the molecular chain of the unsaturated fatty acid contains 2-3 unsaturated CH₂＝CH₂The olefin structure is relatively low in density and is liquid; although the acid value, the saponification value were partially equivalent to those of the saturated fatty acids, and the activity, dispersibility, permeability and reactivity were superior to those of the saturated fatty acids (35.0%, 45.0%, 40.0%, 30.0%, respectively),but the whitening effect is 2.50 to 3.50% lower than that of saturated fatty acids (such as stearic acid, lauric acid, palmitic acid and the like), and especially the oxidation resistance is 2.0 to 3.0 times lower than that of the saturated fatty acids. Although the unsaturated fatty acid has a content of H of 27.5% in the composition of 10-15%₂O₂The whitening effect is also achieved under the condition, but the whitening amplitude is far lower than that of saturated fatty acid (about 2.5-3.5%); and the whiteness of the whitened sample is unstable, and the produced test sample is easy to deteriorate in storage period (only 20-30 days). In this regard, the inventor has fully verified in a large number of comprehensive systematic tests and production processes, and the comprehensive test and production process is more consistent with the general natural law, so that the comprehensive expression of the third exploration basis is applied, and it is more reasonable to select saturated fatty acids such as lauric acid and stearic acid as initial base materials of simulation tests.

Third, the technical scheme

Based on the technical conception, the inventor conducts a large amount of systematic research on the existing raw materials, and in combination with the research content, the inventor conducts self-making or improvement on part of the raw materials. The preparation method of the composite fatty acid color brightness regulator in the embodiment is as follows:

3.1 the main raw materials selected are: sorbitol, stearic acid, lauric acid, ethylene oxide, and the like; the types of auxiliary materials are mainly: xylene, ethanol, butyl stearate, ethyl acetate, EDTA disodium salt, hydrogen peroxide and potassium hydroxide. In addition, sulfuric acid/dodecylbenzene sulfonic acid is also used as a composite catalyst. Furthermore, the composite fatty acid color brightness regulator can also be added with potassium nonylphenol polyoxyethylene (4/10) ether phosphate (NP (4/10) PK) as an antistatic agent, and industrial sodium chloride as an antiseptic stabilizer.

The physical and chemical properties of the various materials selected in the examples of the present invention are set forth in Table 3 below:

TABLE 3 physicochemical indexes of various raw and auxiliary materials selected in the examples of the present invention

3.2 according to the general natural law and the common general knowledge of the basic chemistry and chemical industry, the combination and synthesis of the raw materials selected in the table 3 are reasonable as follows:

3.2.1 Complex fatty acids (C)₁₂/C₁₇) Preparation of secondary esters of sorbitol-reaction of sorbitol with lauric acid, stearic acid

Sorbitol has a compound with 6 hydroxyl-OH structures, has strong hydrophilicity, and can be subjected to esterification reaction with carboxyl-COOH of lauric acid and stearic acid under the catalysis of a catalyst to generate the lauric acid and stearic acid sorbitol secondary ester. Specifically, 0.3mol of stearic acid, 0.3mol of lauric acid and 1.0mol of sorbitol are respectively added in the presence of H₂SO₄The reaction is carried out under the catalysis condition of SAS (linear alkyl benzene sulfonic acid), and the reaction formula is shown as formula (1):

during the experiment, xylene is used as a solvent to dissolve lauric acid and stearic acid respectively, and then the lauric acid and the stearic acid are subjected to esterification reaction with sorbitol respectively. The same synthetic product is obtained in two times of experiments, the two times of experiments are carried out according to the same method, and the obtained product is stored for later use; the two products are preferably stored separately to facilitate observation of the stability of the two synthesized samples and to facilitate regulation and control.

3.2.2C₁₂Saturated fatty acid polyoxyethylene (6) ether and C₁₇Preparation of saturated fatty acid polyoxyethylene (6) ether-polymerization of stearic acid, lauric acid and ethylene oxide respectively

Using dimethylbenzene as a solvent, heating and dissolving lauric acid and stearic acid according to the mole number of 1.0mol respectively, and then naturally cooling and storing for later use.

The polymerization reaction of stearic acid and ethylene oxide under the catalysis of potassium hydroxide KOH is shown as the formula (2):

similarly, the polymerization reaction of lauric acid and ethylene oxide catalyzed by potassium hydroxide is shown as formula (2 a):

the above synthesis principle and method were repeated twice for each of (2) and (2a), and the obtained products were stored in a mixed state.

3.2.3 host Material-disodium ethylenediaminetetraacetate (disodium EDTA) Cross-Linked 2- (4-C)₁₂/C₁₇) Synthesis of composite fatty acid polyoxyethylene (5) ether sorbitol secondary ester

Accurately weighing 1.0mol of EDTA disodium salt, dissolving in 10% potassium hydroxide aqueous solution (about 700-800 g), and adding composite fatty acid (C) under continuous stirring₁₂/C₁₇) A sorbitol secondary ester; the number of molecules is 2.0mol, and the reaction principle equation is shown as the formula (4):

then 2.0mol of polyoxyethylene (5) stearate and 2.0mol of polyoxyethylene (5) laurate are respectively added into the formula < 3 > to obtain the main material of the invention, namely EDTA dipotassium sodium crosslinked 2- (4-C)₁₂/C₁₇) Polyoxyethylene (5) ether sorbitol secondary ester of complex fatty acid. Considering that two CH ═ CH ortho groups in a sorbitol molecule respectively occupy only 0.3mol of lauric acid ester group and stearic acid ester group, and less than the full-position effect of 1.0mol of lauric acid ester and stearic acid ester, after 2.0mol of polyoxyethylene (5) stearate and polyoxyethylene (5) laurate are respectively added, two CH ═ CH ortho groups start formal coordination saturation, and the rest of stearic acid ester and lauric acid ester respectively and stearic acid polyoxyethylene (5) ester start formal coordination saturationThe direct transesterification of ethylene (5) ester and polyoxyethylene (5) laurate, which was verified several times during the synthesis experiments and also according to the general natural law, gives the final product of the formula (4):

(4) by-products of formula (II)

Because the whole reaction system adopts 0.2 percent of H in weight percentage of the total weight of the stearic acid polyoxyethylene (5) ether, the lauric acid polyoxyethylene (5) ether and the two compound fatty acid (C12/C17) sorbitol secondary esters₂SO₄And 2.3% of dodecylbenzenesulfonic acid (SAS) as a catalyst, and in the presence of an alkaline aqueous solution of a mixture of disodium EDTA and KOH, it readily combines with carboxyl groups-COOH in the disodium EDTA and hydroxyl groups-OH in the unreacted sorbitol molecules, and very little potassium dodecylbenzenesulfonate is formed in a coordinated form. The coordination type potassium dodecylbenzene sulfonate existing in a synthesis reaction system has catalytic reaction activity and good dispersibility, and has obvious promotion effect on whitening various plant fibers.

3.2.4 optimized combination of Complex fatty acid color Brightness regulators

As a preferred technical scheme, on the basis of the main material, the composite fatty acid color brightness regulator is prepared from the following raw materials in percentage by weight:

although the product (4) has good whitening function which can replace the existing fluorescent whitening agent, and the reactivity, saponification value and hydrophile lipophilicity (HLB value) of the product are improved to a certain extent, the defects of the product such as refractive index, antistatic property, levelling property, dispersibility, oxidation resistance, redeposition resistance and the like can be further optimized. In order to solve the defects, the inventor tries to adopt the following materials to be compounded with the product (4), and the compatibility of the materials can achieve the following effects in the system:

the addition of butyl stearate can make up the deficiency of refractive index;

the dispersant is added to solve the defect of poor level-dyeing property of the product (4);

the addition of potassium nonylphenol polyoxyethylene (4/10) ether phosphate (NP (4/10) PK) improves the poor antistatic property, anti-redeposition property, dispersibility and the like of the product (4);

adding H with the content of 27.5 percent₂O₂The oxidability, the hydrophilicity and the dispersibility of the mixed system are improved;

and adding ethyl acetate to drop-press the foam formed in the reaction process, so as to increase the flatness and brightness of the surfaces of the finished paper and fabric products.

After the foam of the whole system is completely blown up, the temperature of the whole mixed system is 45-65 ℃, the appearance of the sample is light yellow transparent thick liquid, the pH value is 7.50-8.00, and other various performance indexes are to be measured. After a final sample of this product has been stored at rest for 48 hours, a whitening test is still carried out using mixed waste paper pulp with a whiteness base of 66.0%: adjusting the concentration of paper pulp to 4.50%, stirring at a rotating speed of 60-64 rpm at 35 ℃ for 0.5 hour, wherein the unit dosage of an initial product sample is 1.50Kg/MT (per ton of air-dried pulp), and then, sheet making and drying are carried out to obtain the whiteness increase value of the paper pulp sample of 71.86% -66.0% -5.86%; l is 91.736, a is 0.003, b is 3.34. The test sample of the invention can preliminarily meet the practical requirement of the production process, and basically achieves the expected purpose.

Wherein the compound dispersing agent is preferably compound fatty alcohol polyoxyethylene (6/15) ether sodium sulfonate; which is composed ofPara-octanol polyoxyethylene ether (6) ether and C_12/15The isomerized fatty alcohol polyoxyethylene (15) ether is prepared by sodium sulfite acidification and sodium carbonate neutralization; the secondary octanol polyoxyethylene ether (6) ether and C_12/15The molar ratio of the isomerized fatty alcohol-polyoxyethylene (15) ether is 1: 1; the feeding ratio of the sodium carbonate is the sec-octyl alcohol polyoxyethylene ether (6) ether and C_12/151.0-3.0% of the total weight of the isomerized fatty alcohol polyoxyethylene (15) ether. (ii) a The pH value of the system is controlled to be 6.5 to 7.5.

The potassium nonylphenol polyoxyethylene (4/10) ether phosphate is prepared from nonylphenol polyoxyethylene (4) ether and nonylphenol polyoxyethylene (10) ether through phosphorylation and salifying; the molar ratio of nonylphenol polyoxyethylene (4) ether to nonylphenol polyoxyethylene (10) ether was 1: 1. See patent application No. 2019102878850 for details of the preparation method.

In conclusion, the most typical raw and auxiliary material varieties of the composite fatty acid color brightness regulator are as follows: both have index of refractive index and performance index. The refractive index is mostly in the range of 1.30-1.60, as shown in Table 3, stearic acid, lauric acid and sorbitol which take part in the reaction react to form composite fatty acid (C)₁₂/C₁₇) A sorbitol secondary ester; even in the case of the product of 0.3mol of stearic acid and 0.3mol of lauric acid with 1.0mol of sorbitol, the value of the refractive index was 1.6396 as measured by experimental analysis. Similarly, stearic acid, polyoxyethylene (5) stearate and polyoxyethylene (5) laurate produced by the polymerization reaction of lauric acid and ethylene oxide under the catalysis of KOH have refractive index values of 1.4376 and 1.4653(25 ℃) respectively according to experimental analysis, and are subjected to transesterification reaction with sorbitol stearate, sorbitol laurate, polyoxyethylene (5) stearate and polyoxyethylene (5) laurate in the presence of EDTA disodium salt as a crosslinking agent to produce EDTA disodium salt crosslinked 4- (2-C)₁₂/C₁₇) Complex fatty acid polyoxyethylene (5) ether sorbitol secondary esters; experimental analysis shows that the product has additive effect in refractive index value of 5.8058, and the refractive index value of the by-product of 0.6mol dibasic fatty acid sorbitol secondary ester391; the product of the reaction equation (4) had a total refractive index value of 7.4449. The system contains a very small amount of dodecyl benzene sulfonic acid which is used as a catalyst of a reaction formula (1); the refractive index of the catalyst is in direct proportion to each other in the reaction process of stearic acid and lauric acid in the reaction formula (1); xylene is used as a solvent for dissolving stearic acid and lauric acid in the reaction formulas (1), (2) and (2a), and does not participate in any reaction per se; which itself has a negligible refractive index value. If the actual whiteness gain of the vegetable fibres (wastepaper pulp) is 5.86% according to the experimental results stated in 3.2.4, and the L is 91.736, the pulp concentration is 4.50% according to this conversion, and the temperature is around 30.0 ℃; the whitening time was 0.5 hour, and the total refractive index of the combined product (4) was 7.4449; if the refractive index is understood to be data for every order of magnitude increase, the chemical pulp can be made 1.0% net whiteness improvement, the difference between them is 7.4449-5.86-1.5849. According to the working experience of the inventor, the product < 4 > has whitening effect, but the net increase value of 5.86% is not reached, and only the whiteness value of 70.0% (namely 4.10%) of the whiteness of 5.86% is reached. The net whiteness increase of 5.86% was achieved by adding a mixed system of 1.0mol of butyl stearate, 0.1mol of sodium fatty alcohol polyoxyethylene (6/15) ether sulfonate, 1.0% by mass of potassium nonylphenol polyoxyethylene (4/10) ether phosphate, 14.42% of 27.50% hydrogen peroxide, and 0.3% of ethyl acetate to the product (4). In fact, in the actual production operation process, the whiteness value of the paper pulp is greatly increased depending on the operation modes such as feeding sequence, paper pulp concentration, temperature, whitening time and other factors; especially, the influence of the concentration of the paper pulp on the whitening effect is most obvious; the higher the pulp consistency, the higher the whiteness increase and vice versa. The whitening and color brightness improving effect on the waste paper pulp can be realized by the product (4) and the compounded mixed system because the product of the mixed system does not generate chromophoric groups with glucoside bonds and functional groups of cellulose molecules in fibers, but generates optical isomerization phenomena on the cellulose molecules by virtue of the structural components of other various chemical auxiliary agents in the mixed waste paper, otherwise, whitening and color brightness improving effects cannot be realizedThe effect of brightness, as to how the optical rotatory isomerism phenomenon of the mixed waste pulp fiber is generated, is too complicated to be clarified for the first time and needs to be studied systematically in the future. As can be seen from the mixed system of various basic materials and the synthesized product (4), the composite fatty acid color brightness regulator has excellent refractive index, strong oxidation resistance stability and hard water resistance; hard water resistance up to 600mg/L (as CaCO)₃A durometer).

In addition, regarding the feeding of each reaction formula, the invention adopts the common solvent material of xylene, and the xylene is used for dissolving stearic acid and lauric acid; does not participate in any reaction in the whole synthesis reaction system; and the 10% KOH aqueous solution is used for dissolving EDTA disodium salt and is also used as a solution for adjusting the pH value of the final product of the whole synthesis reaction system. Dissolving potassium atoms in the solution, and carrying out chemical combination on EDTA disodium salt and carboxyl groups of the other two acetic acids in the acetic acid to generate potassium diacetate; potassium sodium originally being Na⁺、K⁺Valuable metal elements, easy to dissolve in water, active in chemical property, and easy to combine or cross-link with any hydroxyl-OH functional group in sorbitol molecule to generate R₁-OCOK-O-R. Of course this is dependent on C₁₂/C₁₇Determining the number of the secondary esters of the composite fatty acid polyoxyethylene (5) ether sorbitol; when C is present₁₂/C₁₇When the number of the secondary ester of the polyoxyethylene (5) ether sorbitol of the compound fatty acid exceeds more than 2, the crosslinking effect with any one of the potassium diacetate is possible. The synthesis product according to equation (1) is a complex fatty acid (C)₁₂/C₁₇) Sorbitol Secondary ester is only an unfinished Primary product, mainly for the purpose of making the product hydrophilic, since sorbitol is a polyhydroxyl-functional compound, strongly hydrophilic, complex fatty acid (C) formed by reaction with 0.3mol stearic acid and 0.3mol lauric acid₁₂/C₁₇) Sorbitol Secondary esters, which the inventors have dosed in this way, are for convenience C₁₂/C₁₇The fatty acid polyoxyethylene (5) ether undergoes a relatively complete transesterification reaction because stearic acid and lauryl alcohol are presentThe acid must not exceed 0.3mol in each occupied position of sorbitol; the transesterification reaction is difficult to proceed constantly beyond this numerical range, resulting in a large amount of water-insoluble C₁₂/C₁₇The composite fatty acid ester by-product is generated, and the whitening effect of the final product, the dispersibility in the pulp solution and the reactivity are directly influenced. The nature of this by-product is in fact that of span-20 and span-60 mixtures. This is visible in the product (4).

According to the reaction formulas (2) and (2a), stearic acid and lauric acid belong to saturated fatty acid, have strong antioxidant stability, and the molecular chain ends of the stearic acid and the lauric acid respectively have a carboxyl-COOH functional group; the functional group has high reactivity, and can easily generate polymerization reaction with ethylene oxide under the catalysis of potassium hydroxide to respectively generate corresponding fatty acid polyoxyethylene ether (ester), the addition number of the ethylene oxide can be adjusted at will by 3-25 of the carboxyl groups of the two fatty acids, the characteristics of the reaction process of the fatty alcohol and the ethylene oxide are basically similar, but one more-C-O is added, and the reactivity of the-C-O in the polymerization process is further increased. This has been well established in a number of scientific experiments and production practices.

According to the reaction formula < 3 > as a preferable example, two complex fatty acids (C) synthesized are used₁₂/C₁₇) Sorbitol secondary ester and EDTA disodium salt are crosslinked to generate two compound fatty acids (C) of EDTA disodium salt type₁₂/C₁₇) The sorbitol secondary ester is used as a structural framework, so that the molecular structure shape and the main components of the product have clear cognition; because the sodium atom in EDTA is cross-linked with any unreacted hydroxyl functional group in sorbitol, two hydrogen atoms are respectively replaced to form covalent bond for coordination, and finally O in hydroxyl is used^2-Atoms and Na in sodium diacetate⁺The combination of the forms of atoms is fully proved in both theoretical principle and actual production operation; as for the use of 10% KOH aqueous solution to dissolve the diacetic acid in EDTA, some of the carboxyl functional groups and K in the diacetic acid⁺Atom(s)It is also reasonable to combine to form potassium diacetate.

Preferably, the reaction formula and the product (4) are two complex fatty acids (C) obtained by sodium salt crosslinking of polyoxyethylene (5) laurate and polyoxyethylene (5) stearate, which are products of the reaction formulae (2) and (2a), with the product EDTA of the reaction formula (3), as monomers₁₂/C₁₇) Sorbitol secondary ester generates ester exchange reaction to generate EDTA disodium salt cross-linking type 2- (4-compound fatty acid (C)₁₂/C₁₇) Polyoxyethylene (5) ether sorbitol secondary ester with by-product 1/3 complex fatty acid (C)₁₂/C₁₇) Sorbitol Secondary ester, when the product of the reaction formula (2), (2a) is smoothly subjected to transesterification with the reaction formula (1) or (3), is due to the synthesized Complex fatty acid (C)₁₂/C₁₇) The position of the ester generated by the reaction with sorbitol is not full, more than 70% of the space needs to be filled with polyoxyethylene laurate (5) ester and polyoxyethylene stearate (5) ester, and the reaction can reach a saturated state at the adjacent positions of two CH (CH) groups, and the reaction form conforms to the generalized natural law and is fully verified in a large amount of industrial production practices and scientific experiments. As to why the control of the one-step mixing and feeding operation was not conducted in the reaction formulas < 1 >, < 2 > and < 2a >, the reason is that the system for producing the product becomes a mixture of polyoxyethylene sorbitol laurate (Tween-20) and polyoxyethylene sorbitol stearate (Tween-60) having similar properties. This mixture can only be used as emulsifier with soap; has no practical effect on whitening and improving color and brightness.

4. Control expression of preparation method of composite fatty acid color brightness regulator

The main material of the invention is EDTA disodium salt crosslinked 2- (4-complex fatty acid (C)₁₂/C₁₇) Polyoxyethylene (5) ether sorbitol secondary ester) which accounts for 72-78% of the total amount of the final system synthesized by the invention. 27.5% H₂O₂The weight percentage of the material is 11-14%; the compound fatty alcohol polyoxyethylene (6/15) ether sodium sulfonate, nonyl phenol polyoxyethylene (4-10) ether phosphate potassium salt, butyl stearate,The total addition amount of ethyl acetate, xylene and the like is small; the proportion of each of the auxiliary materials in the synthesis of the invention is very small, and the materials are added and shaped in sequence. Therefore, the key to control the preparation method of the invention is to synthesize the EDTA disodium salt crosslinked 2- (4-complex fatty acid (C) as the main material₁/C₁₇) Polyoxyethylene (5) ether sorbitol secondary ester. The control and operation modes are as follows:

4.1 Complex fatty acids (C)₁₂/C₁₇) Process and control strategy for sorbitol secondary esters

Weighing stearic acid and lauric acid respectively in 0.3mol and sorbitol in 1.0mol (calculated as 100%) quantitatively and accurately; 0.3mol of lauric acid is added in 0.2% portion of H₂SO₄Reacting with 1.0mol of sorbitol under the catalysis of 3.0 percent of linear alkyl benzene sulfonic acid compound to generate sorbitol secondary ester, reacting for 0.5 hour, and then reacting with sorbitol lauric acid secondary ester by using 0.3mol of stearic acid, wherein the dosage of the two catalysts is unchanged; the reaction temperature is controlled to be 60-80 ℃, the reaction time is controlled to be 1.0 hour, and the product generated when the pH is 4.50-5.00 is dibasic fatty acid (C)₁₂/C₁₇) Sorbitol secondary esters. Before reaction, firstly, respectively heating and dissolving stearic acid and lauric acid by adopting dimethylbenzene, and then putting into use; this is somewhat cumbersome, but easy to operate and control. The addition amount of the dimethylbenzene accounts for 16.95 percent of the total consumption amount of the lauric acid and the stearic acid; the synthesized product is then stored for use.

4.2 polyoxyethylene (5) stearate and polyoxyethylene (5) laurate protocols and control

Firstly, respectively heating and completely dissolving 1mol of stearic acid and 1mol of lauric acid by adopting 16.95% of dimethylbenzene in dosage ratio, and introducing 5.50mol of ethylene oxide addition numbers respectively under the condition of 6.0% of KOH when the respective temperature is reduced to 15-20 ℃; controlling the introduction time to be 3.0 hours, the temperature to be 10 ℃, and the pressure to be 0.5-0.9 Kgf/cm²The pH value is 7.0-7.5; after the reaction is completed, the resulting products are polyoxyethylene (5) stearate and polyoxyethylene (5) laurate. The total reaction process has stearic acid or stearic acid with 1.0 moleculeRespectively carrying out polymerization reaction on the lauric acid and 5.5 molecules of ethylene oxide; the reaction-completed product was then stored for use.

4.3EDTA disodium salt Cross-Linked Complex fatty acid (C)₁₂/C₁₇) Process and control strategy for sorbitol secondary esters

Firstly, 10% KOH aqueous solution is prepared, and the weight ratio of the 1.0mol EDTA disodium salt is 1.0: 2.0, heating to 70-90 ℃, gradually adding all mass numbers of EDTA disodium salt into the hot KOH aqueous solution, and slowly stirring to dissolve the EDTA disodium salt, wherein the pH value of the dissolved EDTA disodium salt and KOH mixed solution is 11.50-12.50, and the temperature is 70-90 ℃; adding two kinds of fatty acids (C) successively and uniformly under continuous stirring₁₂/C₁₇) Sorbitol secondary ester, controlling the temperature within the range of 70-80 ℃, reacting for 0.6 hour at constant temperature, and controlling EDTA disodium salt to crosslink two fatty acids (C)₁₂/C₁₇) The pH value of the sorbitol secondary ester system is 8.50-9.50; if the pH value in the system is lower than 8.50-9.50, a 25% KOH aqueous solution is slowly dripped to adjust the pH value to a specified range, and the temperature of the later period of the system is kept between 65-70 ℃. At the moment, the appearance of the system is in a light yellow transparent liquid state; then the next synthesis reaction is started.

4.4EDTA disodium salt crosslinked 2- (4-Complex fatty acid (C)₁₂/C₁₇) Procedure for synthesis of polyoxyethylene (5) ether sorbitol secondary ester and control law

EDTA disodium salt Cross-Linked Complex fatty acid (C) synthesized at 4.3₁₂/C₁₇) Adding polyoxyethylene (5) stearate and polyoxyethylene (5) laurate on the basis of the sorbitol secondary ester; carrying out ester exchange reaction under the conditions that the pH value is 7.50-8.50 and the temperature is 60-70 ℃; the addition method comprises adding 2.0mol of lauric acid polyoxyethylene (5) ether and EDTA disodium salt crosslinked composite fatty acid (C)₁/C₁₇) Two sorbitol polyoxyethylene (5) laureate esters are formed by transesterification of the first CH ═ CH position of the sorbitol secondary esters with 0.3mol of secondary laurate. When the two are reacted for 0.5 hourThen, two more molecules of polyoxyethylene (5) stearate are added to transesterify with 0.3mol of secondary stearate at the second CH ═ CH position. After reacting for 1.5 hours, the EDTA disodium salt crosslinked 2- (4-complex fatty acid (C) is obtained₁₂/C₁₇) Polyoxyethylene (5) ether sorbitol secondary ester, the whole synthesis reaction is finished.

4.5EDTA disodium salt crosslinked 2- (4-Complex fatty acid (C)₁₂/C₁₇) Determination of physical and chemical performance indexes of polyoxyethylene (5) ether sorbitol secondary ester

EDTA disodium salt crosslinked 2- (4-complex fatty acid (C)₁₂/C₁₇) The polyoxyethylene (5) ether sorbitol secondary ester is a key main material of the invention, the basic feed ratio is 72-78%, the inventor qualitatively and quantitatively analyzes various performance indexes of the main material by adopting a normal experiment mode, and the measured results are as follows:

the appearance of the material is yellow transparent thick liquid measured by a glass culture dish observation method; the pH value of the material is measured to be 8.50 by using pH value test paper; the saponification value of the material is 210mgKOH/g according to the GB/T5534 standard; the total refractive index value of the material is 5.9316 measured according to the GB/T6488 standard; the active matter content of the material is 45.70 percent according to GB/T13173.2 standard, and the dispersibility (dynamic) of the material is 100 percent according to GB/T5550 standard; with 50% H₂O₂The direct oxidation process was carried out at a rate of 1.0: 3.3 ratio oxidation for 100 hours: the quality is not deteriorated; the HLB value of the material is 7.60 through experimental measurement; the effective content of the material is more than 95.0 percent.

4.6 Synthesis of EDTA disodium salt crosslinked 2- (4-Complex fatty acid (C)₁₂/C₁₇) Formula of mixed feeding of polyoxyethylene (5) ether sorbitol secondary ester

Specific details are shown in Table 4

TABLE 4 Synthesis of EDTA disodium salt crosslinked 2- (4-Complex fatty acid (C)₁₂/C₁₇) Formula of mixed feeding of polyoxyethylene (5) ether sorbitol secondary ester

4.7 feeding program and control rule of optimized combined formula of composite fatty acid color brightness regulator

The feed conditions for the optimized combination formula of the composite fatty acid gloss and brightness adjuster are shown in table 5:

TABLE 5 feed conditions for optimized combinations of complex fatty acid gloss and lightness modifiers of the invention

The feeding program and the control rule are as follows:

synthesizing EDTA disodium salt cross-linking type 2- (4-complex fatty acid (C)₁₂/C₁₇) After the polyoxyethylene (5) ether sorbitol secondary ester material is prepared, the temperature of the system is controlled to be 70-80 ℃, and the pH value is 8.0-8.5. Adding quantitative butyl stearate, stirring uniformly, and then sequentially adding quantitative potassium nonylphenol polyoxyethylene (4/10) ether phosphate and composite fatty alcohol polyoxyethylene (6/15) ether sodium sulfonate; after the mixture is uniformly stirred, the temperature of the whole system is kept at 70-80 ℃, and the pH value is kept at 8.0-8.5.

Standing, keeping the temperature for 50 hours, and then naturally cooling; when the temperature of the material system is reduced to 35-40 ℃, a certain amount of 27.5% hydrogen peroxide (H) is added₂O₂) Slowly stirring uniformly, and oxidizing the whole material system; especially for EDTA disodium salt crosslinked 2- (4-complex fatty acid (C)₁₂/C₁₇) Oxidation of polyoxyethylene (5) ether sorbitol secondary esters. The appearance after 0.5 hours of oxidation was a red liquid in appearance and started to produce a large amount of foam. Guiding the expanded foam into another larger stainless steel container for storage, and observing the density, specific surface area and moisture content of the foam; if there is no moisture in the foam and its density begins to decrease, then the foam may be pressed with ethyl acetate; article of justiceWhen no foam is formed in the material system, the oxidation process of the system is indicated to be finished. The ethyl acetate was added dropwise, not in quantitative order. When the foams containing the ethyl acetate component are completely broken into liquid, the liquid is gradually recycled and returned to the original reaction tank for mixing, and the obtained product is the final product. It is worth noting that H is added₂O₂A post oxidation process, essentially an exothermic process; the temperature in the system gradually rises from the original 35-40 ℃ to 65-85 ℃ during oxidation. The ethyl acetate is added, so that the functions of foaming (instead of defoaming) and increasing the refractive index of the product are achieved, and more importantly, the flatness and the light reflection brightness of the surfaces of finished paper and fabric products can be improved by more than 20-30% in the process of using the final product.

4.8 confirmation of quality index of optimized combination formula of composite fatty acid color brightness regulator of the invention

As can be seen from table 5 of the feeding formula synthesized by the optimized combination formula, the feeding ratio of the main material occupies 72-78%, the total feeding of other materials is less, the deviation of the influence range on various quality indexes and physical and chemical performance indexes is small, and indexes such as refractive index, active matter content, dispersibility, hydrophilicity and the like are increased; for example, in a synthesis system of a final product, two auxiliary materials with refractive index indexes, namely butyl stearate (1.4426) with the refractive index of 2.3% and ethyl acetate (1.3730) with the refractive index of more than 1.80%, are added in addition to the refractive index of about 75.0% of the original main material, the net increase value of the refractive index in the system is 2.30% multiplied by 1.4426+1.80 multiplied by 1.3730 to 0.0579, and the original refractive index value in the main material is added to obtain the total refractive index value of a final test product of 5.9895 (only increased by 0.97%), when 2.0 percent of potassium nonylphenol polyoxyethylene (4/10) ether phosphate, 6.0 percent of compound sodium fatty alcohol polyoxyethylene (6/15) ether sulfonate and 12.0 percent of 27.5 percent of hydrogen peroxide are added, the using effect of the optimized combination formula can be obtained, such as active content, dispersibility, HLB value, permeability, stain resistance, and leveling effect, the saponification value in the system is reduced. The numerical ranges of the specific indices are shown in Table 6:

TABLE 6 variation range of the quality index and physical and chemical performance index of the optimized combination formula of the present invention

The terms brightness and whiteness are two completely different concepts according to optical and colorimetry principles. Brightness is an optical index, usually expressed in L-value, and whiteness is a color index, usually expressed in% with MgO as reference; has a whiteness of 90.0% or more, not necessarily a brightness of 98.50L or more; on the contrary, the brightness value is more than 98.50L, and the whiteness value is inevitably more than 93.0%. This is two indicator concepts that must be distinguished.

The data in Table 6 fully reflect the use of the optimized combination formula of the present invention in whitening plant fibers, improving color and brightness, etc., depending on the photochemical properties of the optimized combination formula of the present invention and the partial optical isomerism between the functional groups of the cellulose molecules in the plant fibers and the functional groups of the molecules of the final product of the present invention. The photochemical property of the optical isomerism seems to have an inseparable relation with the active substance content, refractive index, dispersity, stain resistance, oxidation resistance, hard water resistance, even dyeing effect and the like in the quality index of the product; and the product with the anti-fouling function has the functions of static resistance and anti-redeposition.

However, the optimized combination formula according to Table 6 has a saponification value of only 165mgKOH/g, and is not sufficient to completely inhibit the degradation of the glucosidic bonds of cellulose molecules when used as a whitening agent for plant fibers and mixed waste paper pulps, and the washing, decoloring and decontaminating effects of the whitening process are not ideal. The inventors further tried further optimization of the host material. In the aspect of industrial production of the main body material, in order to improve the saponification value of the main body material, the main body material is divided and fed successively in a manner of mixing and dividing the main body material evenly in a mass ratio of 1.0:1.0 in the process of feeding stearic acid and lauric acid. This decreased the mass number and molecular number of stearic acid in the actual reaction, while the mass number and molecular number of lauric acid increased relatively, because the relative mass number of lauric acid was only 70.42% of stearic acid, while the saponification value was 1.31 times that of stearic acid. Estimated from this, if stearic acid and lauric acid are fed in a mass number of 1.0:1.0, the saponification value of the host material system can be increased by 30 to 35%, and the saponification value of the final industrial molded product can be directly increased to 210mgKOH/g or more. The final product of the invention is used for whitening and improving the color and brightness, and not only depends on the content of peroxide and the size of the numerical value of refractive index, but also depends on the advantages and disadvantages of saponification value, washing effect, anti-pollution, antistatic effect and decoloring effect. This experience was observed and summarized by the inventors during a number of commercial production practices and scientific experiments.

In addition, according to table 6, the hydrophilic ratio of the host material was 53.0%, while the lipophilic ratio was 47.0%, and the HLB value was 7.60. The optimum proportion of the hydrophilic part of the main body material of the present invention is 63.0%, the proportion of the lipophilic part is 37.0%, and the HLB value is 8.20, because the main body material component of the present invention is mainly used as a hydrophilic substance, the compatibility of the main body material is required to be improved. The most effective method for improving the compatibility and solubility of the main material is to add 0.5 to 1.0mol of ethylene oxide to participate in polymerization reaction in the process of preparing polyoxyethylene (5) stearate and polyoxyethylene (5) laurate respectively to generate polyoxyethylene (6) laurate with 2.0 molecules and polyoxyethylene (6) stearate with 2.0 molecules, then to participate in ester exchange reaction in the crosslinking process to generate EDTA disodium salt crosslinked 2- (4-complex fatty acid (C)₁₂/C₁₇) A main material of polyoxyethylene (6) ether sorbitol secondary ester. This increases both the active content of the host material and the compatibility of solubility and hydrophilicity of the host material. Through the improvement of the main material, the experiment proves that the hydrophilic proportion of the improved main material is 63.70%, the lipophilic proportion is 36.30%, the HLB value is 8.30, and the rest quality indexes and performance indexesThe expected target values were accurately achieved without change on the basis of table 6.

Specifically, by adjusting the reaction formulas (2) and (2 a): on the basis of table 4, stearic acid and lauric acid were mixed in a mass number of 1.0:1.0, adding 1.0mol of ethylene oxide (i.e. in the preparation of 2.0 month polyoxyethylene (6) laurate and 2.0 molecules of polyoxyethylene (6) stearate, the molar ratio of lauric acid or stearic acid to ethylene oxide is 1: 6), making disodium EDTA salt and two 2-compound fatty acid sorbitol secondary esters undergo the process of cross-linking reaction, then adopting 2.0 molecules of polyoxyethylene (6) laurate and 2.0 molecules of polyoxyethylene (6) stearate to make ester-exchange reaction so as to obtain the invented modified EDTA disodium salt cross-linked 2- (4-compound fatty acid (C)₁₂/C₁₇) A main material of polyoxyethylene (6) ether sorbitol secondary ester. The improved main body material improves the saponification value by 30-35% on the original basis, and the performances of dispersibility, hydrophilicity, compatibility and the like are respectively improved by 25-30%, 35-45% and 30-40%. The structure of the improved host material is confirmed on the basis of formula (4), and can be represented by the following formula (4 a):

the formula (4a) is the EDTA disodium salt crosslinked 2- (4-complex fatty acid (C) as the main material of the invention₁₂/C₁₇) Polyoxyethylene (6) ether sorbitol secondary esters); the mass number of by-products formed after the reaction is significantly reduced by 50.0% compared with formula (4).

The relative molecular weight (molar mass number) of the host material is 2641.57g/mol, if 15% of the by-product relative mass number 408.03g/mol is added, the relative mixed mass number of the host material is 3049.60g/mol, and the experimental analysis result shows that the relative molecular mass number is reduced by 438.79 mass numbers compared with the original relative molecular mass number 3284.36g/mol, which is reasonable and unexpected; the fact that the amount of stearic acid is reduced and the amount of lauric acid is increased means that the mass number of the main material reaction system is reduced to a certain extent, although the polymerization addition number of ethylene oxide is increased, the molar mass number of the ethylene oxide is small, and only 44.053 x 4 is 176.21 g; the defect of the reduction of the whole mass number caused by the reduction of the consumption of stearic acid can not be compensated by far.

In summary, the basic properties of the optimized combination formula finally formulated in the present invention are as follows:

the optimized combined formula of the invention can embody the following excellent performances on mixed waste paper pulp used for secondary fiber, tertiary fiber or n-time fiber and original plant fiber with pollutants:

antistatic Performance (PCD) +/-260-320 mV/kg;

75.0-98.0% of anti-pollution performance;

anti-redeposition performance is 80.0-98.0%;

the improvement rate of the beating degree of the paper pulp is more than or equal to 7.0-10.0%;

the emulsifying and decomposing capacity is more than or equal to 80.0-99.0%;

the HLB value is 9.50-10.00;

35.0-55.0% of hydrophobicity;

inhibiting various degradation efficiencies of cellulose molecules by 70.0-96.0%;

hard water resistance is more than or equal to 1600 ppm;

non-radiative properties, fluorescence value F ═ 0, a ═ 0.001;

the recycling performance is realized, the industrial three-level water can be recycled at will, and the water quality environment and conditions are not limited;

the complex use performance can be freely compounded with anionic and nonionic surfactants and hydrophilic solvents;

the adjustability in the use process is realized by only adopting industrial sodium carbonate to adjust the pH value in a paper pulp system to 7.5-8.0 and then using 27.5 percent hydrogen peroxide to adjust the pH value randomly.

The final confirmed quality index and physical and chemical properties of the main material and the optimized combined formula are shown in table 7.

TABLE 7 confirmation of quality index and Properties of the subject materials and the final products

Description of the drawings: the values in Table 7 show that the results are slightly different from the partial values in Table 6, but the range of variation is not so large

In addition, the practical use effect characteristic parameters of the fluorescent whitening agent and the composite fatty acid gloss and brightness regulator are compared as follows:

the varieties of the fluorescent whitening agent can be more than 10, the specific types are divided into two categories of hydrophilicity and lipophilicity, and the performance characteristics of the fluorescent whitening agent are basically the following common points:

(1) the color coordinates (0.33, 0.46) generated by means of the self molecular structure, which generally refers to the blue, green and red mixed color scale, corresponding to the a value expressed in the present invention, and the white coordinates are generally (0.31, 0.36);

(2) hard water resistance is not achieved, and when the water hardness exceeds 200ppm, only color scale whiteness is achieved, but the real whiteness is achieved;

(3) the reducibility is strong, and the color code effect is lost when the ultraviolet rays or the oxide are seen, and the light and color retention is poor.

A comparison of the parameters of the practical performance characteristics of the fluorescent whitening agent and the composite fatty acid gloss and brightness modifier of the invention is shown in Table 8

TABLE 8 comparison of the results of the performance of the fluorescent whitening agents with the products according to the invention in the course of their practical industrial application

5. The invention relates to a main material and application of an optimized combined formula

The subject materials and optimized composite formulations of the present invention can be used in the following industrial sectors:

5.1 paper industry

The method is suitable for manufacturing finished paper with the whiteness (ISO) of more than 50.0 percent by papermaking; especially, the paper making has strict requirements on the whiteness and the hue of the finished paper; the whiteness value of the finished paper is generally controlled and specified to be 75.0-95.0%, and the color phase is separately specified according to different purposes and application ranges of various types of finished paper. These finished papers mainly comprise: various kinds of paper for daily use, various kinds of paper for culture, various kinds of paper for packaging, various kinds of paper for special use, and the like.

5.2 printing and dyeing industry

The product has multiple purposes in the printing and dyeing industry, and can be used as a whitening agent, a leveling agent, a softening agent, a fabric sizing agent and the like.

5.3 emulsion polymerization and coating industry

Belongs to O/W reactive emulsifier with soap type, and has HLB value of 9.60; the method is suitable for soap-containing emulsion polymerization, such as synthesis of tertiary vinegar, vinyl acetate-acrylate copolymer, pure acrylic, styrene-acrylic, silicone-acrylic, vinyl chloride-acrylate copolymer, ethylene-vinyl acetate copolymer and the like; meanwhile, the rubber emulsion is also an emulsifying dispersant of synthetic rubber and natural rubber; can be used as a whitening agent, an emulsifying dispersant and an anti-settling agent in the coating industry. In addition, the antioxidant can be used as an anti-aging agent and an antioxidant in the high-performance engineering plastic industry.

The following are specific examples of industrial applications.

Example 1

This example shows EDTA disodium salt crosslinked 2- (4-complex fatty acid (C) as the host material₁₂/C₁₇) An example of the preparation of polyoxyethylene (6) ether sorbitol secondary esters is shown in table 9:

TABLE 9 actual feeding formula of main materials for industrial synthesis production

Description of the drawings: the material amount in table 9 is the actual material amount per unit in the process of carrying out the present invention, and each unit is taken as a unit of measurement in the actual production operation process, and each batch of product produced can be composed of 50-100 units.

The operation procedure and control rule of the production process of the main body material are still carried out according to the mode in 4; the reaction principle is also carried out according to the methods of the reaction formulae (1), (2a), (3) and (4). In addition, during the crosslinking reaction, care should be taken to evaporate the water completely in the system to reduce the influence on the purification of the active ingredients of the final product of the present invention, and the temperature of the crosslinking reaction can be raised to more than 100 ℃ if necessary. The commercial production host material in table 9 is a primary amplification. In actual production, the inventor usually adds the actual feeding molecule number n × 10.0 of each raw material in the production process of each batch of products; the total molecular weight reaches 3299.0 mol.

The appearance of the main material is from yellow semitransparent milky liquid to milky pasty thick body (appearance at freezing point), the relative density is 1.037-1.046, the melting point is 110-135 ℃, the freezing point is 15-17 ℃, and the crystallization point is-7 ℃; is miscible in water and is dispersible in water. The product is easy to be mutually soluble with hydrophilic organic solvents such as alcohol, ether and the like, and is insoluble in benzene, toluene, petroleum ether, dichloromethane and various ester hydrophobic organic solvents; the refractive index of the product is eta⁰ _20℃5.9895, respectively; the product has excellent antioxidant stability and hard water resistance; the maximum hard water tolerance limit exceeds 1600 ppm. The product has high chemical reaction activity, and can react with various compounds with-OH, -COOH and-OCH₃、->C＝O、-C＝O、-NH₂The compound monomer functional groups are subjected to various reactions such as grafting, crosslinking and chemical combination, and can react with glucose-O-glycoside bonds in cellulose molecules to form an optical isomerism phenomenon at the temperature of 40-50 ℃, so that the optical isomerism phenomenon can be caused to heavy metal ions such as Ca in water²⁺，Mg²⁺、Fe³⁺、Cu²⁺、Zn²⁺、Pb³⁺、Cr⁵⁺、Ni²⁺Has good chelating effect, and is an O/W type reactive emulsifier with soap, and the HLB value is 8.30.

Example 2

This example uses the disodium EDTA-crosslinked 2- (4-complex fatty acid (C) prepared in example 1₁₂/C₁₇) Polyoxyethylene (6) ether sorbitol secondary esters were the host material and the preparation of the optimized combination formulation was performed as shown in table 10 below:

TABLE 10 optimized combination recipe examples

The above-mentioned feeding procedure, operation and control rules of the optimized combination formula are still performed with reference to the method described in fig. 4. The method is convenient for inhibiting foaming and treating foam in the process of industrial production, when the foam in a material system has a height of 30-50 cm or is about to flow out of a container, a discharge valve at the bottom of the container can be gradually and slowly discharged into another container for storage, so that unnecessary waste of materials is reduced, and the oxidation reaction is further facilitated to be further smoothly carried out due to the addition of a quantitative H₂O₂The foam in the reaction firstly gradually rises from the bottom of the material upwards and also disappears from the bottom. This is the rule of experience and mastery summarized by the inventors from commercial production practice. The whole oxidation reaction time is 5.50-6.0 hours, and the reaction temperature is 80-110 ℃; the reaction characteristic of the oxidation process is exothermic, so that a defined amount of H is added₂O₂When the temperature of the materials is controlled below 40 ℃, the materials can be added, otherwise, the materials are out of control.

Specifically, the industrial production process flow of examples 1 and 2 is mainly divided into the processes of material preparation, preparation of self-made materials, cross-linking reaction, ester exchange reaction, compounding and mixing, oxidation and decoloration, post-treatment, purification treatment and the like, and the whole industrial full-scale production cycle is about 68.5 hours, and is a batch. The control live details are shown in table 11:

TABLE 11 control of the Process in the Industrial production according to the invention

Note: the disodium EDTA salt is used as a cross-linking agent and a stabilizing agent in a mixed system.

The physicochemical properties of the optimized combination formulations of examples 1 and 2 are as follows:

the appearance is light yellow semitransparent milky fluid to milky white paste (at freezing point), and the relative density is 1.067-1.073 g/cm³Melting point of 105-115 ℃, boiling point of 150 ℃, freezing point of 15-17 ℃, crystallization point of-10-20 ℃, and refractive index eta⁰ _20℃6.1375. The product is mixed and dissolved in water; the product is dispersed in water and is alkalescent, is easily soluble with hydrophilic organic solvents such as alcohol, ether and ketone, is only partially soluble with DBE, DMP, DBP, DMF, and is insoluble in hydrophobic organic solvents such as benzene, toluene, turpentine, petroleum ether and halogenated hydrocarbon. The product has excellent oxidation resistance and hard water resistance; the hard water resistance amplitude exceeds more than 1600 ppm/L; the product has excellent emulsifying, dispersing, permeating, dyeing, softening, washing, whitening, antifouling, antistatic and anti-redeposition effects, and belongs to an internal reducing mixture. The product is prepared by polymerizing active materials of main monomers of saturated fatty acid and ethylene oxide, crosslinking the active materials with compound fatty acid sorbitol secondary ester and EDTA disodium salt and performing ester exchange, wherein the system does not contain-SO₃Na，-SO₃H, C is a complex of functional groups such as N, N-O, benzene heterocycle and the like and groups, so that the complex is non-toxic, non-irritant, pollution-free, non-corrosive and non-radiative, and does not produce molecular heredity or cytopathy when contacting with organisms for a long time; since these products have the above-mentioned specific properties, they are often substituted for fluorescent whitening agents such as VBL and UBL …. The product belongs to nonionic surfactant, has HLB value of 9.60 and no CMC value.

The optimized combined formulations prepared in example 2 (examples 1 and 2) were used industrially

One of the examples of industrial applications

The product of the formulation of example 1 was applied to the whitening of fine-faced white board paper and spun cotton, respectively, using a fluorescent whitening agent VBL as a comparative reference, and the known process conditions for both are now described as follows:

for the production of the liner white board, it is known that the whiteness base of the mixed wastepaper pulp is 76.70%, the pulp concentration is 4.30%, and the water hardness (CaCO)₃Calculated) is 270ppm/L, the pH value is 6,50, the whitening time is 0.70 hours, the dosage of the product of the invention and the dosage of VBL of the fluorescent whitening agent are respectively 2.0kg/MT, and 0.01 percent of retention aid and 1.50 percent of dry strength agent are respectively added in the paper making process.

For the whitening of spun cotton (mechanical white fiber), it is known that the whiteness base of cotton is 80.70%, the water hardness is 27.0ppm, and the nominal volume of the whitening tank is 3.0m³The amount of cotton yarn used was 900 kg/tank, to which was added a baume of 46⁰Na of (2)₂SiO₃15.0kg，27.5％H₂O₂20.0kg, wherein the dosage of 98.0 percent of industrial soda ash is 5.0kg, the temperature is 90 ℃, and the whitening time is 1.0 hour; the respective dosage of the fluorescent brightener VBL and the product of the invention is 5,0 kg/tank, and the fluorescent brightener VBL and the product of the invention are used under the same condition; the effects exhibited after use are shown in table 12.

TABLE 12 comparison of the effect of whitening mixed waste pulp and cotton yarn using VBL with example 1

The natural temperature is 45 ℃ under the irradiation of sunlight, the time is 2.0 hours, and the effects are as follows:

from the experimental data in table 12, it can be seen that the difference in the practical use of the fluorescent whitening agent VBL compared to the product of the present invention is quite significant. In addition, a in table 12 indicates that the color of the spectrum is bluish-reddish; b represents the color of the spectrum is yellow; ISO represents the whiteness value; l represents a luminance value; f represents a fluorescence value. Example 1 the hue of yellowish color is relatively rich in hue components, which is different from the concept described in the photoelectric polymer: the functional luminophor of the photoelectric macromolecule is used for generating a color code by means of a conductive form, while the example 1 is mainly realized by means of the refractive index and the oxidation degree of each reaction material, and although the two materials have completely different concepts, the inventor cannot explain the internal relation between the two materials.

Second example of industrial application

Example 2 of a product Synthesis formulation of the present invention applied to a large paper making Enterprise group corporation in Guangdong province for papermaking at a quantitative of 16g/m²，18g/m²And 20g/m²The paper for daily use of (1). It is known that the company produces the three types of domestic paper with the fixed quantity specifications, and the company hopes to use the three types of non-deinked waste paper to produce the A-grade domestic paper with the simulated wood pulp quality. The three waste papers respectively account for the following proportions: 25.0% of paperboard paper, 45.0% of yellow crystal card and 30.0% of white waste paper edge. The whiteness base of three mixed broke pulps is known to be 78.65%. NaOH and 27.5% H were used, respectively₂O₂The pulp was crushed at unit dosages of 12.0kg/MT and 15.0kg/MT, respectively. After pulping, washing, pulping and whitening; 0.8kg/MT dispersant and 8.0kg/MT wet strength agent are added into the whitened pulp, 2.0kg/MT VBL and 2 example products of the invention are respectively used, and the water hardness of pulping water is 460 ppm/L; the whiteness and the hue were measured by sampling the finished paper produced by papermaking, and the results are shown in Table 13:

TABLE 13 VBL compares the usage effect of the paper made of the wood-like pulp of example 2

The data in tables 12 and 13 of the above application examples one and two fully indicate that: the VBL of the fluorescent brightener has almost no practical whitening effect on the fiber containing mechanical fibers or under the condition that the water quality hardness value is more than 300ppm/L, the displayed whiteness value shows almost no real whiteness value except the fluorescence whiteness value, and the light and color retention is poor when the light and color retention is seen in sunlight; is very unstable; the actual use effects of the invention in example 1 and example 2 are just opposite. As can also be seen from tables 12 and 13, the practical effects and the whitening magnitude of examples 1 and 2 of the present invention are consistent with the foregoing demonstration.

Third example of industrial application

The high-grade coated white board paper is produced and operated by a medium-sized paper industry company in Jiangxi of China and is used for manufacturing high-grade packaging products. The enterprise hopes to adopt the product of the invention to replace a fluorescent whitening agent VBL for whitening coating glue (paint); the variety of the coating produced by the enterprise is known to be divided into a top coating and a bottom coating, and the solid content of the coating is respectively 50% (surface) and 55% (bottom); the extender pigment and the coloring pigment used were 450 mesh/cm, respectively²Ground calcium carbonate and 700 mesh/cm²The calcined kaolin is prepared from the following raw materials in a mass ratio of 1.0: 1.0; the used base material is carboxylic styrene-butadiene latex, and the dosage is respectively 200kg/T and 250 kg/T; the type of the used dispersing agent is sodium polyacrylate, and the using amount is 0.1-0.15%; the product example 1 of the present invention and the fluorescent whitening agent VBL were used in a unit amount of 3.0kg/T (wherein the product example 1 of the present invention was used only for the top coat), and then coated, dried, and cured during the papermaking process to make a coated white board. The results of the production application are shown in table 14:

TABLE 14 comparison of the actual use of VBL for making fine coated white board paper as in example 1

The index data for the two entries in table 14 need to be explicitly stated: 1. the less the amount of the coating film used per unit area, the stronger the covering power of the coating film and the lower the use cost; 2. the higher the surface uniformity of the coating film, the brighter the surface of the finished paper, and the higher the whiteness value and the L value. The good dispersing power of example 1 can thus be demonstrated again.

It should be added here that, from the beginning, the inventors performed a series of exploratory simulation and comparison experiments on the subject material of the present invention, and these experimental data are greatly different from table 9 and the corresponding quality index data, but indicate directions for implementing the technical solution of the present invention, specifically as shown in table 15:

TABLE 15 simulation of the comparative mode (sample of 66.0% brightness of the spent pulp used in an amount of 1.5Kg/MT)

Note: the preparation method of the main body materials 1-4 comprises the steps of directly mixing the raw materials; the preparation of the host materials 5-8 is carried out as described in reference to fig. 4.

The environment protection condition of the industrial production of the composite fatty acid color brightness regulator (main material and optimized combined formula) of the invention is as follows:

the composite fatty acid color brightness regulator can completely ensure no air pollution, no noise interference and no sewage discharge in the industrial production process, basically avoids the pollution caused by three wastes and does not generate any other negative effect; it can be seen from the physicochemical parameters of the raw material variety and the operation procedure and control rule of the production process used in the implementation process of the present invention, even if water used for cleaning the reaction equipment container occasionally exists, the KOH solution can be used for dissolving and preparing 10% KOH solution, and no water is discharged. Moreover, the product of the invention is nontoxic, non-irritant, non-inflammable, non-explosive, safe and clean, even if the product is used for whitening by users, the aerobic amount in papermaking circulating water is naturally increased to 30-40 mg/L, the increase of COD in the papermaking sewage treatment process is also inhibited, the reduction range of NH-N can reach 50-70%, and the product is fully verified in a large number of industrial production practice processes.

In conclusion, the inventors have found that the properties of the various materials of the composite fatty acid gloss and brightness regulator, including the materials selected and used in the light of the physicochemical properties and defects of the fluorescent whitening agentThe method prepares a main body material (EDTA disodium salt cross-linked 2- (4-complex fatty acid (C)) which has internal reduction property and chelating function and can generate optical isomerism with cellulose molecules by taking the principle that residual lignin in mixed waste paper pulp is effectively removed by means of activation, permeation, level dyeing, anti-pollution, anti-static, anti-redeposition and the like by starting from a material with refractive index₁₂/C₁₇) Polyoxyethylene (6) ether sorbitol secondary ester), and finally, the expected purpose to be achieved is achieved by the theoretical viewpoints of compound shaping, oxidation and decoloration post-treatment and the like of the main body material, namely, the mixed waste paper fiber and the mechanical fiber for papermaking can improve the whiteness ISO and the L value and the a and b values, and have pure natural artistic feeling, and the research and exploration mode undoubtedly has important value and is a product variety with great development prospect, popularization and application.

Compared with the prior art, the compound fatty acid color brightness regulator has the most prominent advantages and differences that: according to the soap laundry principle and photochemical property, materials with refractive index are adopted to respectively carry out double combination and ester exchange reaction to prepare a main body material, and the refractive index is improved to promote the brightness L value and whiteness of the plant fiber; furthermore, the brightness, whiteness, permeability, dispersibility, leveling property, stain resistance, oxidation resistance, antistatic property and redeposition resistance of the product system are further improved by adopting materials such as butyl stearate, a dispersing agent, potassium nonylphenol polyoxyethylene (4/10) phosphate and the like; the advantages are complementary, and the application effects of internal reduction and external oxidation are stably realized; excellent whiteness stability and gloss and color retention. The implementation of this technical solution is highly innovative in itself. In addition, the composite fatty acid color brightness regulator product is sold and used in the market in large scale in an industrialized mode, is well received by users, and achieves certain economic and social benefits; rather than wandering in the laboratory.

All the technical features of the embodiments described above can be combined arbitrarily, and for brevity of description, all the possible combinations of the technical features in the embodiments described above are not described, so long as those skilled in the art can implement the technical solution according to the concept principles of the present invention, and even some contents can be innovated. However, as long as there is no contradiction between combinations of these technical features, the scope of the present specification should be considered as being described.

The above-mentioned embodiments only express several embodiments of the present invention, and the description thereof is more specific and detailed, but not construed as limiting the scope of the invention. It should be noted that, for a person skilled in the art, several variations and modifications can be made without departing from the inventive concept, which falls within the scope of the present invention. Therefore, the protection scope of the present patent shall be subject to the appended claims.

Claims

1. The composite fatty acid color brightness regulator is characterized by comprising a main material, butyl stearate, nonylphenol polyoxyethylene (4/10) ether phosphate potassium salt and a dispersing agent; the main material consists of compound fatty acid sorbitol secondary ester and C₁₂Saturated fatty acid polyoxyethylene (6) ether and C₁₇Saturated fatty acid polyoxyethylene (6) ether is crosslinked;

wherein the compound fatty acid in the compound fatty acid sorbitol secondary ester is C₁₂Saturated fatty acids and C₁₇A saturated fatty acid; the cross-linking agent adopted for cross-linking is EDTA disodium salt.

2. The compound fatty acid color brightness regulator according to claim 1, wherein C is₁₂The saturated fatty acid is lauric acid; and/or the presence of a catalyst in the reaction mixture,

said C is₁₇The saturated fatty acid is stearic acid.

3. The compound fatty acid color brightness regulator according to claim 1, wherein said compound fatty acid sorbitol secondary ester, C₁₂Polymerization of saturated fatty acidsOxyethylene (6) ether, C₁₇The molar ratio of the saturated fatty acid polyoxyethylene (6) ether to the crosslinking agent is 1.5-2.5: 1.5-2.5: 1.5-2.5: 1.

4. the compound fatty acid color brightness regulator according to claim 1, wherein the preparation method of the compound fatty acid sorbitol secondary ester comprises the following steps:

said C is₁₂Saturated fatty acid, C₁₇Carrying out esterification reaction on saturated fatty acid and sorbitol under the catalysis of a catalyst to obtain the product; said C is₁₂Saturated fatty acid, C₁₇The molar ratio of saturated fatty acid to sorbitol is 0.2-0.4: 0.2-0.4: 1.

5. the compound fatty acid color brightness regulator according to claim 1, wherein C is₁₂Saturated fatty acid polyoxyethylene (6) ether is prepared from C₁₂Saturated fatty acid and ethylene oxide are polymerized; said C is₁₂The molar ratio of saturated fatty acid to ethylene oxide is 1: 6; and/or the presence of a catalyst in the reaction mixture,

said C is₁₇Saturated fatty acid polyoxyethylene (6) ether is prepared from C₁₇Saturated fatty acid and ethylene oxide are polymerized; said C is₁₇The molar ratio of saturated fatty acid to ethylene oxide is 1: 6.

6. the composite fatty acid color and brightness regulator as claimed in claim 1, wherein the potassium nonylphenol polyoxyethylene (4/10) ether phosphate is prepared by phosphatizing and salifying polyoxyethylene nonylphenol (4) ether and polyoxyethylene nonylphenol (10) ether; the molar ratio of the nonylphenol polyoxyethylene (4) ether to the nonylphenol polyoxyethylene (10) ether is 0.8-1.2: 0.8-1.2.

7. The composite fatty acid color and brightness regulator according to claim 1, wherein the dispersant is composite fatty alcohol polyoxyethylene (6/15) ether sodium sulfonate composed of sec-octanol polyoxyethylene ether (6) ether and C_12/15Isomerization of fatty alcohol polyoxyethylene (15) ether to sulfurous acidSodium acidification and sodium carbonate neutralization; the secondary octanol polyoxyethylene ether (6) ether and C_12/15The molar ratio of the isomerized fatty alcohol-polyoxyethylene (15) ether is 0.8-1.2: 0.8-1.2.

8. The composite fatty acid color brightness regulator according to any one of claims 1-7, characterized in that it is prepared from raw materials comprising, in weight percent:

9. the method for preparing a composite fatty acid gloss adjuster according to claim 8, comprising the steps of:

obtaining the main material, controlling the temperature to be 70-80 ℃ and the pH value to be 8-8.5, adding the butyl stearate, stirring, adding the potassium nonylphenol polyoxyethylene (4/10) ether phosphate and a dispersing agent, maintaining the temperature to be 70-80 ℃ and the pH value to be 8-8.5, reacting for 45-55 hours, and cooling;

10. Use of the complex fatty acid gloss control agent of any one of claims 1-8 in paper making, printing, emulsion making or coating.