CN103667548B - A kind of synthetic sperm oil fat liquoring complex agent and preparation method thereof - Google Patents

Abstract

The invention provides a synthetic cetyl oil compound fatliquoring agent and a preparation method thereof. Concretely comprise following steps: (1) add oleic acid and catalyzer, heat up to 90 ℃, add polyethylene glycol within 1 hour, the mol ratio of oleic acid and polyethylene glycol is 1: 1.05, and the consumption of catalyzer is total material 0.1-0.5% of the mass; (2) Then heat up to 150-200 ° C, and vacuum dehydration, react for 2-5 hours, check the acid value every 1 hour until there is no change, and measure the water solubility, after passing Cool down to below 40 DEG C and filter catalyst discharge, obtain the synthetic cetyl oil of reddish-brown transparent oily liquid; (3) add the oxazolidine of 10-15% of synthetic cetyl oil quality, the polyether modification of 2-5% Silicone oil and 5-10% sulfited fish oil are compounded, then deionized water is added to adjust the solid content to 50%, and a reddish-brown transparent synthetic cetyl oil compound fatliquor is obtained.

Description

A kind of synthetic cetyl oil compound fatliquoring agent and preparation method thereof

technical field

The invention relates to a synthetic cetyl oil compound fatliquoring agent and a preparation method thereof, belonging to the technical field of leather chemical industry.

Background technique

Cetyl oil contains more than 70% long-chain fatty alcohol esters of unsaturated fatty acids. This special chemical structure determines that it can endow the leather with a good oily and waxy feeling in addition to the softness and plumpness it should have. , other fatliquors do not have this feature. However, due to the scarcity of whale resources and the limitation of hunting, the source of natural spermaceti oil is very scarce, and people have begun to develop synthetic spermaceti oil. Synthetic cetyl oil is mainly formed by the esterification reaction of oleic acid, linoleic acid, etc. In the chemical method, toluene is often added as a water-carrying agent, and the reflux or decompression reaction is carried out in the presence of a catalyst. After the reaction, the solvent needs to be recovered, which requires high sealing of the equipment, and the reaction temperature of different catalysts and the appearance of the product are quite different, such as When using p-toluenesulfonic acid as a catalyst, it only needs to react at 120°C, but the color of the product is very dark. In addition, the price of oleyl alcohol is very high, more than 40 yuan/kg, and domestic resources are scarce, so it needs to be imported, and the cost is unbearable. To adapt to sales for reducing costs, the synthetic cetyl oil components contained in many commercially available synthetic cetyl oil fatliquoring agents are very limited.

CN101948714 mentions that synthetic cetyl oil is a kind of oily wax ester, which itself does not contain surface active groups and cannot be effectively combined with leather. It is usually emulsified by means of external surfactants or chemically modified to introduce surface active groups. active group. The first method has no binding force with leather and is easy to wash off, while the second method can be combined with leather collagen fibers, so many studies tend to chemically modify it. The traditional chemical modification methods mainly include sulfation modification, sulfur trioxide sulfonation modification and oxidative sulfitation modification. Among them, sulfation modification is more corrosive to equipment, and waste acid water needs to be separated for static treatment. The performance of acid resistance and electrolyte resistance is also very poor, making the product difficult to promote. The synthetic cetyl oil product sulfonated by sulfur trioxide has stable emulsion, strong acid resistance, chromium powder resistance and electrolyte resistance, fine emulsion particles, and good permeability. However, this method requires large equipment investment and needs to be close to the sulfuric acid production plant. Obtaining cheap sulfur trioxide raw materials is difficult to popularize in leather chemical enterprises. Modification by oxidative sulfitation method is to change the double bonds in the synthetic cetyl oil into more reactive epoxy bonds with air blowing, and then use sulfitation reagents for ring-opening reaction. The product performance is the same as that of the sulfonation method. Close, sulfiting reagents are also cheaper, but there will be irritating sulfur dioxide odor in the product, which needs to be removed by vacuuming, and sulfite residues in the product will cause the product to precipitate saturated brine as the storage time prolongs .

Contents of the invention

The purpose of the invention is to provide a kind of synthetic cetyl oil composite fatliquoring agent and preparation method thereof for the deficiency of traditional synthetic cetyl oil and modified products thereof. The invention adopts polyethylene glycol instead of oleyl alcohol to carry out esterification reaction with oleic acid to prepare synthetic cetyl oil, and then mixes active ingredients such as oxazolidine, polyether modified silicone oil, sulfited fish oil and the like to compound. Adopt self-made solid acid catalyst during esterification, its preparation method is as the method mentioned in CN02151526.3, polyethylene glycol has good wetting and softness, and the price is cheaper, and is widely used in industries such as leather textile printing and dyeing, such a The cost is greatly reduced, and the composition of synthetic cetyl oil can also be greatly improved when compounding the fatliquoring agent. Moreover, polyethylene glycol has strong hydrophilicity and does not need to be separated. The synthetic cetyl oil obtained by this method has good self-emulsifying ability, and does not need to add emulsifier or chemically modify it, which greatly simplifies this type of fatliquoring agent. preparation. The reaction process adopts intermittent vacuum to remove water, which avoids the harm of using solvent as water-carrying agent. The finally obtained fatliquor product has good emulsion stability, good comprehensive fatliquor performance, and the finished leather has good oily and waxy feeling, and good softness and fullness.

The technical scheme adopted by the present invention to realize the above-mentioned purpose of the invention is:

A kind of synthetic cetyl oil compound fatliquoring agent and preparation method thereof, comprises the steps:

(1) Add oleic acid and catalyst, heat up to 90°C, add polyethylene glycol within 1 hour, the molar ratio of oleic acid to polyethylene glycol is 1:1.05, and the amount of catalyst is 0.1-0.5 of the total mass of the material %;

(2) Then heat up to 150-200°C, vacuumize and dehydrate, react for 2-5 hours, check the acid value every 1 hour until there is no change, and measure the water solubility, cool down to below 40°C and filter the catalyst after passing the test Blowing, obtain the synthetic cetyl oil of reddish-brown transparent oily liquid. The catalyst can be recycled 8-10 times in the experiment;

(3) Add 10-15% oxazolidine, 2-5% polyether modified silicone oil and 5-10% sulfited fish oil of synthetic cetyl oil quality to compound, then add deionized water to adjust to 50 % solid content, obtain the reddish-brown transparent synthetic cetyl oil compound fatliquoring agent.

In the above preparation method, the polyethylene glycol is any one or a mixture of PEG400, PFG600, and PEG800.

In the above preparation method, the catalyst is a self-made solid acid catalyst, and the amount of the catalyst is 0.1-0.5% of the total mass of the material, preferably 0.2-0.3%.

In the above preparation method, the oxazolidine is ZOLDINEZE of Dow Chemical Company, and the dosage is 10-15% of the quality of synthetic cetyl oil, preferably 12-13%.

In the above preparation method, the polyether modified silicone oil is DC-190 of Dow Corning Company, and the dosage is 2-5% of the quality of synthetic cetyl oil, preferably 2.5-3.5%.

In the above preparation method, the sulfited fish oil is LUTAPOLTIS of Lihou Chemical Company, and the dosage is 5-10% of the quality of synthetic cetyl oil, preferably 6-8%.

In order to investigate the fatliquoring effect of this synthetic cetyl oil compound fatliquor, the present invention investigates by following application examples.

Application example: goatskin garment leather

Take one piece of wet-blue goatskin embryo, cut it in half, slice it, peel it evenly, and mark it as A and B respectively. Add 8% synthetic cetyl oil compound fatliquoring agent to A skin, and add 8% to B skin Commercially available cetyl oil fatliquor.

Process conditions:

Weighing: Accurately weigh the tare weight as the basis for the materials used in the following processes

(Note: L-6, PR are retanning agent products of our company)

detailed description

The present invention is specifically described below by way of examples. However, it should not be understood that the scope of the above-mentioned themes of the present invention is limited to the following embodiments, and all technologies realized based on the content of the present invention belong to the scope of the present invention.

Example 1

(1) Add 70kg of oleic acid and 0.5kg of catalyst, heat up to 90°C, and add 105kg of polyethylene glycol PEG400 within 1 hour.

(2) then be warming up to 180 ℃, react 3 hours, acid value no longer changes, water solubility is qualified, be cooled to below 40 ℃ and filter catalyst discharge, obtain the synthetic cetyl oil of reddish-brown transparent oily liquid.

(3) Add 16kg of oxazolidine, 3.5kg of polyether modified silicone oil and 12kg of sulfited fish oil, then add 161kg of deionized water to adjust to a content of 50%, to obtain a reddish-brown transparent synthetic cetyl oil. Fat agent 367.5kg.

The test results after the application test are shown in Table 1.

Table 1 Skin sample test results

project A B National standard Moisture content and volatile matter/% 14 13.1 12-20 Dichloromethane extract/% 18.1 16.5 12-19 Tensile strength/(N/mm ² ) 23.7 16.8 ≥10 Elongation at break/% 124 82 35-55 Crack height/mm 21.3 14.4 ≥7 Tear strength/(N/mm) 56.7 38.7 ≥20

Example 2

(1) Add 70kg of oleic acid and 0.4kg of catalyst, heat up to 90°C, add polyethylene glycol PEG40060kg and PEG80045kg within 1 hour.

(2) then be warming up to 175 ℃, react 4 hours, acid value no longer changes, and water solubility is qualified, be cooled to below 40 ℃ and filter catalyst discharge, obtain the synthetic cetyl oil of reddish-brown transparent oily liquid.

(3) Add 22kg of oxazolidine, 7kg of polyether modified silicone oil and 168kg% sulfited fish oil of synthetic cetyl oil quality, then add 168kg of deionized water to adjust to 50% content, to obtain reddish-brown transparent synthetic Cetyl oil compound fatliquor 379kg.

The test results after the application test are shown in Table 2.

The detection result of table 2 skin sample

project A B National standard Moisture content and volatile matter/% 14.6 13.1 12-20 Dichloromethane extract/% 18.3 16.5 12-19 Tensile strength/(N/mm ² ) 24.3 16.8 ≥10 Elongation at break/% 117 82 35-55 Crack height/mm 23.5 14.4 ≥7 Tear strength/(N/mm) 57.2 38.7 ≥20

Claims (5)

1. a preparation method for synthesizing cetyl oil composite fatliquoring agent, is characterized in that comprising the steps: (1) Add oleic acid and solid acid catalyst, heat up to 90 ° C, add polyethylene glycol within 1 hour, the molar ratio of oleic acid and polyethylene glycol is 1: 1.05, and the consumption of catalyst is 0.1% of the total mass of the material -0.5%; (2) Then heat up to 150-200°C, vacuumize and dehydrate, react for 2-5 hours, check the acid value every 1 hour until there is no change, and measure the water solubility, cool down to below 40°C and filter the catalyst after passing the test Blowing, obtain the synthetic cetyl oil of reddish-brown transparent oily liquid, catalyst is recycled 8-10 times in the experiment; (3) Add 10-15% oxazolidine, 2-5% polyether modified silicone oil and 5-10% sulfited fish oil of the quality of synthetic cetyl oil to compound, then add deionized water to adjust to the quality Ratio is the content of 50%, obtains the synthetic spermaceti oil compound fatliquoring agent of reddish-brown transparent. 2. the preparation method of a kind of synthetic cetyl oil composite fatliquor according to claim 1 is characterized in that described polyethylene glycol is any one or several mixtures in PEG400, PEG600, PEG800. 3. the preparation method of a kind of synthetic cetyl oil composite fatliquor according to claim 1 is characterized in that described oxazolidine is the ZOLDINEZE of Dow Chemical Company. 4. the preparation method of a kind of synthetic cetyl oil composite fatliquoring agent according to claim 1 is characterized in that described polyether modified silicone oil is the DC-190 of Dow Corning Company. 5. the preparation method of a kind of synthetic cetyl oil composite fatliquoring agent according to claim 1 is characterized in that described sulfited fish oil is the LUTAPOLTIS of power thick chemical company.