CN104888658A - Collagen based organic silicon surfactant and preparation method thereof - Google Patents

Abstract

The invention relates to a collagen-based silicone surfactant and a preparation method thereof, belonging to the field of protein-based surfactants; it is characterized in that collagen polypeptide (hydrolyzate) is used as a hydrophilic chain and siloxane is used as a hydrophobic chain, and it also belongs to organic Silicon surfactant field. The steps of the preparation method of the collagen-based silicone surfactant of the present invention include: (1) dissolving the collagen polypeptide (or hydrolyzate) in distilled water to prepare an aqueous collagen polypeptide (or hydrolyzate) solution; (2) dissolving the epoxy polydimethylformaldehyde Dissolve the epoxy-based polydimethylsiloxane in an organic solvent to obtain an organic solution; (3) Add the above-mentioned epoxy-based polydimethylsiloxane organic solution into the collagen polypeptide (or hydrolyzate) aqueous solution, and stir at 40~50°C for reaction 5~10 hours. After the reaction is completed, the collagen-based silicone surfactant is obtained through separation and purification such as extraction, distillation and freeze-drying. The surfactant prepared by the method has good surface activity and can be used in the fields of detergents, emulsifiers, personal care products, textile auxiliaries, leather auxiliaries and the like.

Description

A kind of collagen-based silicone surfactant and preparation method thereof

technical field

The invention relates to a collagen-based silicone surfactant and a preparation method thereof, belonging to the field of preparation of protein-based surfactants and silicone surfactants.

Background technique

Surfactants are an important class of fine chemicals, which were mainly used in washing and textile industries in the early days, and now their application range covers almost all fields of fine chemicals. In the 21st century, with the shortage of petroleum resources and a series of environmental problems brought about by over-exploitation and application, finding environmentally friendly renewable surfactant raw materials has become an important research topic. Protein-based surfactant is an ideal environment-friendly surfactant. Protein-based materials are mainly derived from animals and plants, which are rich in raw materials and easy to degrade. Their special molecular structure and properties can also enable surfactants to obtain special functions. At present, the United States, Germany and Japan all have protein-based surfactant products with international influence, and the most typical one in China is the synthetic detergent Remy, which is prepared by condensation reaction of the hydrolyzate obtained by hydrolyzing skin collagen with strong alkali and oleoyl chloride. Bang A. Recently, it has been reported that collagen polypeptide-based surfactants prepared by hydrolyzing dander with alkaline protease to obtain collagen polypeptides with small molecular weight and then condensed with oleoyl chloride (Chi Yuanlong, Cui Min, Liao Xuepin, etc. The synthesis process of collagen polypeptide-based surfactants Optimization [J]. China Leather, 2011,40 (23):8-11), and the protein-type anionic surfactant prepared by the reaction of waste wool alkali hydrolyzed amino acid polypeptide, waste silk alkali hydrolyzate and oleoyl chloride (strong Xi Huai, Feng Hongyan, Zhang Hui. Preparation of protein-based surfactants from waste wool[J]. Leather and Chemical Industry, 2010, 27(6):6-8; Wang Zhao, Qiang Xihuai, Xia Qingyou, etc. Preparation of waste silk Process technology of protein-based surfactants [J]. Sericulture Science, 2013, 39(4): 0778-0782.), etc. It can be seen that protein-based surfactants have become a research hotspot today. However, they all adopted oleoyl chloride, and the hydrophobic parts of the prepared protein-based surfactants were all high-level fatty long chains.

With the rapid development of the leather industry, a large amount of leather scraps are inevitably produced in the leather manufacturing process. Among them, the chromium-free pre-tanning leather scraps are rich in collagen, have a single component, and are not polluted, so that high-quality, high-purity collagen materials can be produced. If this resource can be fully utilized, it will greatly promote the conservation of resources and the improvement of the environment. Collagen has good moisture absorption and moisturizing properties, biocompatibility and biodegradability. It can improve the performance of collagen through the reaction of its surface active groups such as amino groups and carboxyl groups, so that it can be used in different fields. For example, the aldehyde group of glutaraldehyde is used to react with the primary amino group of collagen to improve the mechanical properties of collagen and applied to biomaterials (Olde Damink L H H, Dijkstra P J, Van Luyn M J A, et al. Glutaraldehyde as a crosslinking agent for collagen-based biomaterials[J]. Journal of Materials Science: Materials in Medicine, 1995, 6(8): 460-472), using the amino reaction between genipin and collagen to improve its mechanical stability and thermal stability It is used in the field of three-dimensional biological scaffold materials, and the primary amines of γ-(2.3 glycidoxy)propyltrimethoxysilane containing epoxy groups and collagen or its hydrolyzates have been studied more in recent years. Glyco- and carboxyl-group reactions are used in the field of biological tissue engineering (Tonda-Turo C, Cipriani E, Gnavi S, et al. Crosslinked gelatin nanofibres: Preparation, characterization and in vitro studies using glial-like cells[J]. Materials Science and Engineering: C, 2013, 33(5): 2723-2735), etc. It can be seen that collagen can be improved or endowed with excellent properties through chemical modification, so as to be applied in different fields. However, there are no patents and reports on the preparation of surfactants using organosilicon-modified collagen.

Silicone surfactant is a type of surfactant composed of polydimethylsiloxane as the hydrophobic chain, and the methyl group at the middle or terminal position is replaced by one or more hydrophilic groups. It has the characteristics of low surface tension, good wetting and spreading, basically physiological inertia, strong emulsification and good compatibility, and is widely used in textiles, leather, daily chemicals, coatings and other fields. Due to the special structure of its hydrophobic group, silicone surfactants have excellent surface activity, which is lower than the surface tension of traditional hydrocarbon surfactant aqueous solutions. Nowadays, it has become a development trend to use renewable biomass resources to prepare silicone surfactants. Such as the hydrosilylation reaction of the synthesized glycoside compounds containing unsaturated bonds and hydrogen-containing silicone oil (Feng Wu. Synthesis and characterization of β-cyclodextrin side-group polysiloxane[J]. Daily Chemical Industry, 2008, 38(4): 214-218), or glycosides prepared by reacting polysiloxanes or monomers containing carboxyl, hydroxyl and other groups with saccharide compounds containing corresponding reactive groups and then undergoing an equilibrium reaction Modified silicone surfactant; sugar amide modified silicone surfactant prepared by reaction of amino polysiloxane with sugar lactone, or reaction of epoxy-modified polysiloxane with amino sugar (such as chitosan) ( Wagner R , Wersig R , Schmaucks G, et al . Siloxanyl group containing anionic polyhydroxy compounds for use as surfactants[P]. DE 4318539 , 1994-12-8; Dietz T , Gruning B , Lersch P , et al . Organopolysiloxanes comprising polyhydroxyorganyl radicals and polyoxyalkylene radicals[P]. US 5891977 , 1999-04-06.), and so on. They have both the advantages of silicone surfactants and biosurfactants, can reduce the surface tension to about 30 mN/m, and have good application prospects.

In view of this, the preparation of collagen-based silicone surfactants by chemically reacting silicones containing active groups with collagen can effectively improve the surface activity of protein-based surfactants. It can be seen that the preparation method of the present invention can improve the utilization rate of resources, the process is simple, environmental protection, the product is mild, the stability is good, and the application prospect is broad.

Contents of the invention

Aiming at the prior art, in order to realize effective utilization of resources and effectively reduce environmental pollution, the present invention provides a collagen-based silicone surfactant and a preparation method thereof. The method is simple and easy to operate, and the product has high surface activity and good application prospect.

The purpose of the present invention is achieved by the following technical measures.

The collagen-based silicone surfactant of the present invention has the following structural formula of formula I.

Among them, R ₁ and R ₂ in the structural formula I are the collagen polypeptide (hydrolyzate) in the following scheme II; R ₃ and R ₄ are one of H and collagen polypeptide (hydrolyzate), and at least one of them is collagen polypeptide (hydrolyzate) ; The value of n is an integer from 1 to 50.

The preparation method of the collagen-based silicone surfactant of the present invention comprises the following steps, wherein the parts of the raw materials are parts by mass unless otherwise specified.

The preparation method of the collagen-based organosilicon surfactant prepared by providing hydrophilic chains with collagen polypeptide (or hydrolyzate) and hydrophobic chains with epoxy polydimethylsiloxane comprises the following steps.

(1) Add 100 parts of collagen polypeptide (or hydrolyzate) to 900 parts of distilled water, stir and dissolve at 35-45°C for 0.5-1.0 hour to obtain collagen polypeptide (or hydrolyzate) aqueous solution.

(2) Dissolve 1~5 parts of epoxy polydimethylsiloxane in 30~50 parts of organic solvent, stir at room temperature to dissolve completely.

(3) Add the collagen polypeptide (or hydrolyzate) aqueous solution obtained in step (1) into a three-necked flask, heat to 40~50°C, and add dropwise the epoxy polydimethylsiloxane obtained in step (2) while stirring Organic solution of alkane, after adding, react for 5-10 hours.

(4) Add the reaction product obtained in step (3) into a Soxhlet extractor, extract with 50-100 parts of carbon tetrachloride for 24-48 hours, and remove unreacted organosiloxane. Then under 8.0KPa, 30~50℃ under reduced pressure distillation for 2~4 hours to remove the organic solvent. Finally, the collagen-based silicone surfactant was obtained by freeze-drying.

Collagen polypeptide (or hydrolyzate) is obtained from waste leather (pigskin, cowhide or sheepskin, etc.) before tanning in the leather industry through acid, alkali or enzymatic degradation methods.

The molecular weight of collagen polypeptide (or hydrolyzate) is any one of 1000~20000 Da.

Epoxy polydimethylsiloxane is any one of single-end epoxy polydimethylsiloxane, double-end epoxy polydimethylsiloxane, and side chain epoxy polydimethylsiloxane .

In the molecular structure formula of epoxy-based polydimethylsiloxane, the degree of polymerization of the polydimethylsiloxane chain link is an integer of 1 to 50, that is, the molecular weight is any one of 300 to 4000 Da.

Organic solvent is any one in acetone, Virahol, ethanol.

The addition ratio of epoxy polydimethylsiloxane and collagen polypeptide (or hydrolyzate) (calculated based on the active groups contained) is epoxy: amino (molar ratio) = 0.5:1~2:1.

Performance Testing.

1. The surface tension is measured by the hanging sheet method (Wang Shirong et al. Surfactant Chemistry [M]. Chemical Industry Press, 2010, 11), the test instrument model: QBZY-1 automatic surface tension meter.

2. The determination of the critical micelle concentration adopts the surface tension method (Zhao Guoxi. Physical Chemistry of Surfactants [M]. Peking University Press, 1991, 182).

3. The determination of HLB value adopts emulsification method (K. Gupta R, James K, J. Smith F. Sucrose esters and sucrose ester/glyceride blends as emulsifiers[J]. Journal of Oil & Fat Industries, 1983, 60(4) :862-869.).

4. Fourier transform infrared spectrometer was used for group analysis, model of infrared spectrometer: Spectrum One, scanning range: 4000 ~500cm ^-1 . The test results are shown in Figure 1. 1261 cm ^-1 and 1000~1100 cm ^-1 are the characteristic absorption peaks of Si-CH ₃ and Si-O-Si respectively. By comparing the infrared spectra of collagen polypeptide (or hydrolyzate) and collagen-based silicone surfactant, it can be proved that organosiloxane has chemically reacted with collagen polypeptide (or hydrolyzate).

5. The determination of emulsifying performance is based on the method of literature (Mao Peikun. Industrial Analysis of Synthetic Detergents [M]. China Light Industry Press, 1988.471). Add 10ml soybean oil and 10ml, 5g/L surfactant into a dry stoppered measuring cylinder, mix well and then place it in a 40°C water bath, invert the measuring cylinder 10 times every 15 minutes, a total of 5 times. Then it was left to stand in a water bath at 40° C. for 24 hours, and the emulsification efficiency of the surfactant was observed and calculated.

The present invention has the following advantages.

1. The hydrophobic organosiloxane chain link is connected to the hydrophilic collagen polypeptide (or hydrolyzate) through a chemical reaction, and the resulting product has amphiphilic properties and is an excellent macromolecular surfactant.

2. The present invention uses collagen polypeptide (or hydrolyzate) with rich sources of raw materials and good degradation performance as the raw material, which has a positive effect on the full utilization of resources and improvement of the environment.

3. The present invention can prepare protein-based silicone surfactants with different surface activities, such as emulsifying, foaming, Surface tension, etc., to meet the application requirements in different fields and specific application conditions.

Description of drawings

Accompanying drawing 1 is the infrared comparison diagram of Example 1 and collagen polypeptide (or hydrolyzate).

Detailed ways

The present invention is described in detail by the following examples. It is necessary to point out that this example is only used to further illustrate the present invention, and can not be interpreted as limiting the protection scope of the present invention. Those skilled in the art can use the above-mentioned invention Some non-essential improvements and adjustments have been made to the content.

Example 1.

Dissolve 100 parts of collagen polypeptide (or hydrolyzate) (molecular weight is about 1500 Da) in 900 ℃ distilled water at 40 ℃ to make a 10% aqueous solution. Adjust the pH to 9~10 with 1M NaOH. Dissolve 1.7 parts of double-ended epoxy polydimethylsiloxane (molecular weight: 362Da) in 30 parts of isopropanol, and add the resulting organic solution dropwise into the collagen polypeptide (or hydrolyzate) aqueous solution, and stir at 40°C React for 10 hours. It was then extracted with 50 parts of carbon tetrachloride for 48 hours to remove unreacted siloxane. Distill at 40°C and 0.8KPa for 4 hours to remove residues of isopropanol and carbon tetrachloride. Finally, it was freeze-dried at -55°C to remove excess water, and the collagen-based silicone surfactant (CBES-1) was obtained.

Example 2.

Dissolve 100 parts of collagen polypeptide (or hydrolyzate) (molecular weight is about 1500 Da) in 900 ℃ distilled water at 40 ℃ to make a 10% aqueous solution. Adjust the pH to 9~10 with 1M NaOH. Dissolve 1.7 parts of double-ended epoxy polydimethylsiloxane (molecular weight: 362Da) in 30 parts of isopropanol, and add the resulting organic solution dropwise into the collagen polypeptide (or hydrolyzate) aqueous solution, and stir at 40°C After reacting for 5 hours, the pH was adjusted to 4-5 with 1M hydrochloric acid solution, and the reaction was continued for 5 hours before ending. It was then extracted with 50 parts of carbon tetrachloride for 48 hours to remove unreacted siloxane. Distill at 40°C and 0.8KPa for 4 hours to remove residues of isopropanol and carbon tetrachloride. Finally, it was freeze-dried at -55°C to remove excess water, and the collagen-based silicone surfactant (CBES-2) was obtained.

Example 3.

Dissolve 100 parts of collagen polypeptide (or hydrolyzate) (molecular weight is about 20,000Da) in 900°C distilled water at 40°C to make a 10% aqueous solution. Adjust the pH to 9~10 with 1M NaOH. Dissolve 1.7 parts of double-ended epoxy polydimethylsiloxane (molecular weight: 362Da) in 30 parts of isopropanol, and add the resulting organic solution dropwise into the collagen polypeptide (or hydrolyzate) aqueous solution, and stir at 40°C React for 10 hours. It was then extracted with 50 parts of carbon tetrachloride for 48 hours to remove unreacted siloxane. Distill at 40°C and 0.8KPa for 4 hours to remove residues of isopropanol and carbon tetrachloride. Finally, it was freeze-dried at -55°C to remove excess water, and the collagen-based silicone surfactant (CBES-3) was obtained.

Example 4.

Dissolve 100 parts of collagen polypeptide (or hydrolyzate) (molecular weight is about 20,000Da) in 900°C distilled water at 40°C to make a 10% aqueous solution. Adjust the pH to 9~10 with 1M NaOH. Dissolve 1.7 parts of double-ended epoxy polydimethylsiloxane (molecular weight: 362Da) in 30 parts of isopropanol, and add the resulting organic solution dropwise into the collagen polypeptide (or hydrolyzate) aqueous solution, and stir at 40°C After reacting for 5 hours, the pH was adjusted to 4-5 with 1M hydrochloric acid solution, and the reaction was continued for 5 hours before ending. It was then extracted with 50 parts of carbon tetrachloride for 48 hours to remove unreacted siloxane. Distill at 40°C and 0.8KPa for 4 hours to remove residues of isopropanol and carbon tetrachloride. Finally, it was freeze-dried at -55°C to remove excess water, and the collagen-based silicone surfactant (CBES-4) was obtained.

Example 5.

Dissolve 100 parts of collagen polypeptide (or hydrolyzate) (molecular weight is about 1500 Da) in 900 ℃ distilled water at 40 ℃ to make a 10% aqueous solution. Adjust the pH to 9~10 with 1M NaOH. Dissolve 1.7 parts of double-terminal epoxy polydimethylsiloxane (molecular weight is about 4000Da) in 30 parts of isopropanol, and then add the obtained organic solution dropwise to the collagen polypeptide (or hydrolyzate) aqueous solution, at 40 ° C The reaction was stirred for 10 hours. It was then extracted with 50 parts of carbon tetrachloride for 48 hours to remove unreacted siloxane. Distill at 40°C and 0.8KPa for 4 hours to remove residues of isopropanol and carbon tetrachloride. Finally, it was freeze-dried at -55°C to remove excess water, and the collagen-based silicone surfactant (CBES-5) was obtained.

Example 6.

Dissolve 100 parts of collagen polypeptide (or hydrolyzate) (molecular weight is about 20,000Da) in 900°C distilled water at 40°C to make a 10% aqueous solution. Adjust the pH to 9~10 with 1M NaOH. Dissolve 1.7 parts of double-terminal epoxy polydimethylsiloxane (molecular weight is about 4000Da) in 30 parts of isopropanol, and then add the obtained organic solution dropwise to the collagen polypeptide (or hydrolyzate) aqueous solution, at 40 ° C The reaction was stirred for 10 hours. It was then extracted with 50 parts of carbon tetrachloride for 48 hours to remove unreacted siloxane. Distill at 40°C and 0.8KPa for 4 hours to remove residues of isopropanol and carbon tetrachloride. Finally, it was freeze-dried at -55°C to remove excess water, and the collagen-based silicone surfactant (CBES-6) was prepared.

Table 1 is the surface tension, critical micelle concentration and HLB test results

Claims (8)

1. a collagen-based organic silicon surfactant, is characterized in having any one in following molecular structural formula I:

Wherein R ₁, R ₂for the collagen polypeptide (hydrolysate) of following schematic diagram II; R ₃, R ₄for a kind of in H, collagen polypeptide (hydrolysate), and has one at least for collagen polypeptide (hydrolysate); N value is the integer of 1 ~ 50.

。

2. collagen-based organic silicon surfactant according to claim 1, is characterized in that preparation method comprises the following steps (wherein said raw material number, except specified otherwise, is mass fraction):

(1) preparation of collagen polypeptide (or hydrolysate) aqueous solution:

100 parts of collagen polypeptides (or hydrolysate) are joined in 900 parts of distilled water, in temperature 35 ~ 45 DEG C of stirring and dissolving 0.5 ~ 1.0 hour, obtains collagen polypeptide (or hydrolysate) aqueous solution;

(2) preparation of epoxy radicals dimethyl silicone polymer organic solution:

1 ~ 5 part of epoxy radicals dimethyl silicone polymer is dissolved in 30 ~ 50 parts of organic solvents, after stirring at normal temperature is dissolved completely, obtains epoxy radicals dimethyl silicone polymer organic solution;

(3) preparation of collagen-based organic silicon surfactant:

Collagen polypeptide (or hydrolysate) aqueous solution step (1) obtained joins in there-necked flask, is heated to 40 ~ 50 DEG C, then under agitation drips the epoxy radicals dimethyl silicone polymer organic solution that step (2) obtains, adds rear continuation reaction 5 ~ 10 hours;

(4) purification of collagen-based organic silicon surfactant:

The product that step (3) obtains is joined in apparatus,Soxhlet's, extract 24 ~ 48 hours with 50 ~ 100 parts of carbon tetrachloride, remove unreacted organosiloxane, again under 8.0 kPa, 30 ~ 50 DEG C of decompression distillation, 2 ~ 4 hours removing organic solvents, then freeze drying obtains collagen-based organic silicon surfactant.

3. collagen-based organic silicon surfactant according to claim 1, is characterized in that: in molecular structural formula, the molecular weight of collagen polypeptide (or hydrolysate) chain link is any one in 1000 ~ 20000 Da.

4. collagen-based organic silicon surfactant according to claim 1, is characterized in that: in molecular structural formula, the degree of polymerization of PolydimethylsiloxaneChain Chain joint is the integer of 1 ~ 50, and namely molecular weight is any one in 300 ~ 4000 Da.

5. the preparation method of collagen-based organic silicon surfactant according to claim 2, it is characterized in that in described step (1), collagen polypeptide (or hydrolysate) is that before tanning with leather industry, discarded skin (pigskin, ox-hide or sheepskin etc.), for raw material, obtains through acid, alkali or enzymic degradation method.

6. the preparation method of collagen-based organic silicon surfactant according to claim 2, is characterized in that described step (2) epoxy group dimethyl silicone polymer is any one in single-ended epoxy dimethyl silicone polymer, both-end epoxy dimethyl silicone polymer, side group epoxy dimethyl silicone polymer.

7. the preparation method of collagen-based organic silicon surfactant according to claim 2, is characterized in that in described step (2), organic solvent is any one in acetone, isopropyl alcohol, ethanol.

8. the preparation method of collagen-based organic silicon surfactant according to claim 2, is characterized in that the adding proportion (calculating with contained active group) of described step (3) epoxy group dimethyl silicone polymer and collagen polypeptide (or hydrolysate) is epoxy radicals: amino (mol ratio)=0.5:1 ~ 2:1.