CN114621397B - Thickener for no-wash hand-washing liquid system and preparation method and application thereof - Google Patents
Thickener for no-wash hand-washing liquid system and preparation method and application thereof Download PDFInfo
- Publication number
- CN114621397B CN114621397B CN202011456184.4A CN202011456184A CN114621397B CN 114621397 B CN114621397 B CN 114621397B CN 202011456184 A CN202011456184 A CN 202011456184A CN 114621397 B CN114621397 B CN 114621397B
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- CN
- China
- Prior art keywords
- thickener
- chain segment
- diisocyanate
- micelle
- leave
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
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- 239000007788 liquid Substances 0.000 title claims abstract description 33
- 238000005406 washing Methods 0.000 title claims abstract description 16
- 238000002360 preparation method Methods 0.000 title description 9
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- 239000000693 micelle Substances 0.000 claims abstract description 29
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- 150000001875 compounds Chemical group 0.000 claims abstract description 16
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- 238000006116 polymerization reaction Methods 0.000 claims description 20
- 239000002904 solvent Substances 0.000 claims description 20
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 claims description 16
- RRAMGCGOFNQTLD-UHFFFAOYSA-N hexamethylene diisocyanate Chemical compound O=C=NCCCCCCN=C=O RRAMGCGOFNQTLD-UHFFFAOYSA-N 0.000 claims description 14
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- NIMLQBUJDJZYEJ-UHFFFAOYSA-N isophorone diisocyanate Chemical compound CC1(C)CC(N=C=O)CC(C)(CN=C=O)C1 NIMLQBUJDJZYEJ-UHFFFAOYSA-N 0.000 claims description 4
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- KXBFLNPZHXDQLV-UHFFFAOYSA-N [cyclohexyl(diisocyanato)methyl]cyclohexane Chemical compound C1CCCCC1C(N=C=O)(N=C=O)C1CCCCC1 KXBFLNPZHXDQLV-UHFFFAOYSA-N 0.000 claims description 3
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- GNDOBZLRZOCGAS-UHFFFAOYSA-N 2-isocyanatoethyl 2,6-diisocyanatohexanoate Chemical compound O=C=NCCCCC(N=C=O)C(=O)OCCN=C=O GNDOBZLRZOCGAS-UHFFFAOYSA-N 0.000 claims description 2
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- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 3
- UPMLOUAZCHDJJD-UHFFFAOYSA-N 4,4'-Diphenylmethane Diisocyanate Chemical compound C1=CC(N=C=O)=CC=C1CC1=CC=C(N=C=O)C=C1 UPMLOUAZCHDJJD-UHFFFAOYSA-N 0.000 description 3
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- 239000000243 solution Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 201000010740 swine influenza Diseases 0.000 description 1
- 238000001308 synthesis method Methods 0.000 description 1
- KSBAEPSJVUENNK-UHFFFAOYSA-L tin(ii) 2-ethylhexanoate Chemical compound [Sn+2].CCCCC(CC)C([O-])=O.CCCCC(CC)C([O-])=O KSBAEPSJVUENNK-UHFFFAOYSA-L 0.000 description 1
- IMNIMPAHZVJRPE-UHFFFAOYSA-N triethylenediamine Chemical compound C1CN2CCN1CC2 IMNIMPAHZVJRPE-UHFFFAOYSA-N 0.000 description 1
- AVWRKZWQTYIKIY-UHFFFAOYSA-N urea-1-carboxylic acid Chemical compound NC(=O)NC(O)=O AVWRKZWQTYIKIY-UHFFFAOYSA-N 0.000 description 1
- 229920003169 water-soluble polymer Polymers 0.000 description 1
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F283/00—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G
- C08F283/006—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G on to polymers provided for in C08G18/00
- C08F283/008—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G on to polymers provided for in C08G18/00 on to unsaturated polymers
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- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
- A61K8/00—Cosmetics or similar toiletry preparations
- A61K8/18—Cosmetics or similar toiletry preparations characterised by the composition
- A61K8/72—Cosmetics or similar toiletry preparations characterised by the composition containing organic macromolecular compounds
- A61K8/81—Cosmetics or similar toiletry preparations characterised by the composition containing organic macromolecular compounds obtained by reactions involving only carbon-to-carbon unsaturated bonds
- A61K8/8105—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
- A61K8/8117—Homopolymers or copolymers of aromatic olefines, e.g. polystyrene; Compositions of derivatives of such polymers
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- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
- A61K8/00—Cosmetics or similar toiletry preparations
- A61K8/18—Cosmetics or similar toiletry preparations characterised by the composition
- A61K8/72—Cosmetics or similar toiletry preparations characterised by the composition containing organic macromolecular compounds
- A61K8/81—Cosmetics or similar toiletry preparations characterised by the composition containing organic macromolecular compounds obtained by reactions involving only carbon-to-carbon unsaturated bonds
- A61K8/8141—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides or nitriles thereof; Compositions of derivatives of such polymers
- A61K8/8152—Homopolymers or copolymers of esters, e.g. (meth)acrylic acid esters; Compositions of derivatives of such polymers
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- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61Q—SPECIFIC USE OF COSMETICS OR SIMILAR TOILETRY PREPARATIONS
- A61Q19/00—Preparations for care of the skin
- A61Q19/10—Washing or bathing preparations
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- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
- A61K2800/00—Properties of cosmetic compositions or active ingredients thereof or formulation aids used therein and process related aspects
- A61K2800/40—Chemical, physico-chemical or functional or structural properties of particular ingredients
- A61K2800/48—Thickener, Thickening system
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- Organic Chemistry (AREA)
- Dermatology (AREA)
- Agricultural Chemicals And Associated Chemicals (AREA)
- Polyurethanes Or Polyureas (AREA)
Abstract
The invention discloses a thickener for a no-clean hand sanitizer system, which comprises a polymer main chain, a solvation chain segment and a micelle chain segment, wherein the solvation chain segment is freely stretched in the no-clean hand sanitizer system, the micelle chain segment is insoluble in the no-clean hand sanitizer system, the solvation chain segment and the micelle chain segment are connected through a compound structure containing hydroxyl groups and double bonds, and the thickener for the no-clean hand sanitizer system has the following structure:
Description
Technical Field
The invention relates to the field of preparation of high polymer materials, in particular to a thickener for a no-clean hand sanitizer system, and a preparation method and application thereof.
Background
Along with the gradual improvement of environmental awareness and the strict national requirements on environmental protection, the topics of 'saving water resources' and 'protecting environment' are gradually accepted and popularized by people, and in the fields of personal care and family care, the rapidly-developed no-clean hand sanitizer can effectively save precious water resources, beautify our environment, and has the advantages of convenient carrying and taking along with use, thus being popular and loved by people. Especially, during the period of the new coronaries pneumonia in 2020, the hand-washing-free liquid can be said to isolate viruses, an effective sterilization means for protecting people is provided, and the acceptance of the hand-washing-free liquid in the market is greatly improved.
Leave-on hand washes are typically composed of water, alcohol, and a thickener, where alcohol is the primary sterilizing ingredient. The hand-washing-free liquid soap has the following advantages: 1. washing hands without water: the use and the carrying are convenient; the hands can be cleaned anytime and anywhere without washing; 2. the continuous action is as follows: the effect lasts for a long time, and the effect can last for 4-5 hours and can reach 6 hours at the maximum; 3. soft skin care: has effects in controlling hand oxidative stress level, preventing skin injury and protecting hand, and caring hand skin. 4. Virus killing and sterilization: proved by the disease prevention control center in the national academy of military medicine and Hubei province, the inactivated virus (poliovirus, H1N1 influenza A virus, avian influenza H5N1 virus and hand-foot-mouth (EV 71) virus) has the killing rate of 99.99 percent. After being checked by the disease prevention and control center of Anhui province, the product can kill staphylococcus aureus and escherichia coli after being diluted by 10 times.
The traditional thickening agent for the water-containing system is mainly water-soluble polymer, has a completely hydrophilic molecular structure, does not contain a hydrophobic structure, such as cellulose (HEC) and acrylic thickening Agent (ASE), and achieves the aim of thickening the water phase through forming hydrogen bonds with water molecules in the system.
Polyurethane thickeners are a class of thickeners developed in the 80 s of the 20 th century, and are water-soluble oligomers containing hydrophobic groups. The main structure of the thickener is that the thickener contains a hydrophilic main component part, wherein the hydrophilic main component part is a hydrophilic polymer chain which is connected with a hydrophobic group through a covalent bond to form the associative thickener. In aqueous systems, the hydrophilic portion of such thickeners ensures dissolution or dispersion of the thickener molecules in water by forming hydrogen bonds with the water; in an aqueous system, hydrophobic parts on the thickener are bridged to emulsion, solid particles and micelles which can form hydrophobic association in the aqueous system to form a space three-dimensional network structure, so that the thickening of the aqueous system is realized. Such thickeners can be classified as hydrophobic alkali swellable thickeners (HASE) and polyurethane associative thickeners (HEUR) and other types of associative thickeners. The aqueous system added with HEUR has more excellent leveling property, excellent coating film fullness and high film-forming gloss, so that the aqueous system is widely applied.
CN101633718A discloses a comb polyurethane associative thickener, a preparation method and application thereof. In the patent, a chain extender containing a hydrophobic long chain is synthesized, and the hydrophobic chain segment is increased by introducing the chain extender into the thickener molecule, so that the thickening effect is improved. However, the synthesis of the chain extender is relatively complex.
EP1765900 describes thickeners based on aqueous formulations of nonionic water-dispersible or water-soluble polyurethanes having a specific structure. The specific structure of these polymers is achieved by the presence of allophanate linkages which are created by the use of excess isocyanate. As component (a) hydrophilic polyols having at least 2 OH groups may be used, which may additionally contain ether groups.
CN 103755861 discloses a carbomer, which is mainly prepared by polymerizing acrylic acid in a mixed solvent of water and tert-butanol using a water-soluble initiator to obtain a powdery carbomer. According to the method, a green friendly aqueous phase reaction system with better inclusion is provided by adding tertiary butanol, and carbomer with high quality performance is obtained.
CN103483491 discloses a preparation method of powder carbomer, which is mainly to polymerize acrylic acid in a mixed solvent of ethyl acetate and cyclohexane by adopting an oil-soluble initiator to obtain white powdery polyacrylic acid powder, and has better thickening effect in the fields of water phase and personal care.
US3912921 discloses a substance obtained by copolymerizing acrylic acid and acrylic acid ester (the alkyl group contains 10-30 carbon atoms), a mixture of a polymer and a solvent is obtained by free radical polymerization in a solvent system, and finally a powdery acrylic acid ester copolymer is obtained by processes such as separation, washing, drying and the like, which can obtain a good thickening effect in water.
The thickener products described in the above patents can be used in aqueous systems for various applications. The polyurethane thickener disclosed in CN101633718A and EP1765900 is difficult to thicken in a wash-free liquid system with high ethanol content, and cannot meet the use requirement; the carbomer thickeners of the invention of CN 103755861, CN103483491 and US3912921 can meet the annual requirements of the hand washing-free liquid soap, but the carbomer thickeners have higher price and complex process, and hardly meet the market requirements.
The development of thickeners that can meet the high ethanol system is therefore becoming the focus of current research.
Disclosure of Invention
The invention aims at solving the problems of the prior thickener and providing a novel thickener for a no-clean hand sanitizer system. According to the invention, the basic principle of thickening the polyurethane thickener in the water phase is adopted, the micelle chain segments comprising the solvation chain segments and the performance association structure which can be freely stretched in the no-clean hand-washing liquid system are obtained through polymerization, the three-dimensional net structure can be established by association coordination in the high-ethanol system, the movement of free molecules in the system is restrained, the viscosity of the product is greatly improved, and the requirement of the use viscosity of the no-clean hand-washing liquid is met. In addition, the ideal viscosity can be obtained by adding a small amount of the product into a formula system.
In order to achieve the above object, the present invention has the following technical scheme:
a thickener for a leave-on hand sanitizer system, the thickener comprising a solvating segment in a polymer backbone which is freely extendable in the leave-on hand sanitizer system and a micelle segment which is insoluble in the leave-on hand sanitizer system, the solvating segment and the micelle segment being connected by a hydroxyl-and double bond-containing compound structure, the thickener for a leave-on hand sanitizer system comprising the following structure:
wherein,
a is a residue of a polyisocyanate and,
b is a polyether polyol residue,
d is a compound residue containing hydroxyl and double bonds,
e is a micelle chain segment structure insoluble in a no-wash hand-washing liquid system,
m is any integer from 1 to 5.
According to the thickener for the no-clean hand sanitizer system, provided by the invention, the solvation chain segment which can be freely stretched in the no-clean hand sanitizer system and the micelle chain segment which is insoluble in the no-clean hand sanitizer system are introduced into the molecular main chain of the polyurethane thickener, so that the main chain segment can be effectively stretched in the system, the micelle chain segment can be in a performance association type micelle structure, a dense three-dimensional net structure is built in the system, meanwhile, the solvation chain segment can be in good hydrogen bond interaction with water and ethanol in the system, the number of molecules capable of freely moving in the system is reduced, and the viscosity of the system is effectively improved.
In the present invention, the polyisocyanate related to the polyisocyanate residue a is a diisocyanate and/or a triisocyanate, and preferably the polyisocyanate is a diisocyanate.
For example, suitable isocyanates may be 1, 5-naphthalene diisocyanate, 4' -diphenylmethane diisocyanate (MDI), xylylene Diisocyanate (XDI), tetramethylxylylene diisocyanate (TMXDI), 4' -diphenyldimethylmethane diisocyanate, 4-dibenzyl diisocyanate, 1, 3-xylylene diisocyanate, 1, 4-xylylene diisocyanate, isomers of Toluene Diisocyanate (TDI), 1-methyl-2, 4-diisocyanatocyclohexane, 1, 6-diisocyanato-2, 4-trimethylhexane, 1-isocyanatomethyl-S-isocyanato-1-trimethylcyclohexane, 4' -diisocyanatophenyl perfluoroethane, tetramethoxybutane-1, 4-diisocyanate, butane-1, 4-diisocyanate, hexane-1, 6-diisocyanate (HDI), isophorone diisocyanate (IPDI), dicyclohexylmethane diisocyanate, cyclohexane-1, 4-diisocyanate, ethylene diisocyanate, phthalic acid di-isocyanatoethyl ester.
In the present invention, the diisocyanate is one or more of aliphatic diisocyanate, alicyclic diisocyanate and aromatic diisocyanate.
In some embodiments, the aliphatic diisocyanate groups of the present invention may be, for example, 1, 4-butylene diisocyanate, 1, 12-dodecylene diisocyanate, 1, 10-decamethylene diisocyanate, 2-butyl-2-ethylpentamethylene diisocyanate, 2, 4-or 2, 4-trimethylhexamethylene diisocyanate, and hexamethylene diisocyanate (1, 6-hexamethylene diisocyanate, HDI). Furthermore, the alicyclic diisocyanates are isophorone diisocyanate (IPDI), 2-isocyanatopropyl cyclohexyl isocyanate, 4-methylcyclohexane-1, 3-diisocyanate (H-TDI) and 1, 3-di (isocyanatomethyl) cyclohexane. In addition, diisocyanates such as 4,4 '-methylenebis (cyclohexyl isocyanate) (also known as dicyclohexylmethane-4, 4' -diisocyanate) or 2, 4-methylenebis (cyclohexyl) diisocyanate, which are also known as "saturated MDI", can also be present as groups in the polyurethanes according to the invention. The isocyanate plays a role in connection in the polymer, and different units can be grafted on the main chain, so that the isocyanate can produce a combined effect to meet the performance requirement of the invention.
Preferably, wherein the aliphatic diisocyanate is selected from one or more of 1, 6-Hexamethylene Diisocyanate (HDI), isophorone diisocyanate (IPDI) and dicyclohexylmethane diisocyanate (HMDI);
preferably, wherein the aromatic diisocyanate is selected from Toluene Diisocyanate (TDI) and/or 4, 4-diphenylmethane diisocyanate (MDI).
In the invention, the triisocyanate is one or more of 4,4' triphenylmethane triisocyanate, 2-isocyanatoethyl 2, 6-diisocyanatohexanoate and HDI trimer.
In the present invention, the polyether polyol related to the polyether polyol residue B is one or more of polyethylene glycol (PEG), polypropylene glycol (PPG), polyethylene glycol-polypropylene glycol (PEG-PPG) and polytetramethylene glycol, preferably polyethylene glycol (PEG).
In the present invention, the polyether polyol has a molecular weight of 2000 to 20000 daltons, preferably 4000 to 8000 daltons.
The hydroxyl-containing olefinic compounds referred to by the hydroxyl-containing and double bond-containing compound residue D of the present invention include, but are not limited to, hydroxyethyl (meth) acrylate, hydroxypropyl (meth) acrylate, polyethylene glycol (meth) acrylate, 9-alkenyl-12-hydroxyoctadecanoic acid, and the like, or combinations thereof. The compound containing hydroxyl and double bond mainly plays a role in connection, and the solvated chain segment and the micelle chain segment are effectively connected to realize the thickening effect.
The micelle chain segment structure insoluble in the hand-washing-free liquid system is mainly formed by polymerizing acrylic monomer styrene and/or methyl methacrylate; when polystyrene and polymethyl methacrylate reach a certain molecular weight, the polystyrene and polymethyl methacrylate are not dissolved in ethanol, the same washing-free hand sanitizer system with higher ethanol content (volume fraction is about 75%) is also not dissolved, and the polystyrene and polymethyl methacrylate can react with solvation chain segments to form micelles, so that a three-dimensional network structure of the system is established, and the viscosity of the whole system is improved.
The micelle chain segment structure insoluble in the hand-washing-free liquid soap system has the molecular weight of 200-15000 daltons, preferably 4000-11000 daltons. When the molecular weight of the micelle chain segment is smaller, a micelle with stable structure cannot be formed with other micelle chain segments, and when the molecular weight is larger, the micelle chain segment curls to form an intramolecular micelle; neither of these structures provides a good thickening effect on the system.
The free radical initiator selected in the invention comprises at least one of organic peroxide compound, azo compound, inorganic persulphate compound and hydrogen peroxide, or the optional combination thereof, wherein the free radical initiator comprises but is not limited to azodiisobutyronitrile, azodiisoheptonitrile, benzoyl peroxide, lauroyl peroxide, ammonium persulfate, sodium persulfate and hydrogen peroxide. Benzoyl peroxide is preferred as its free radical initiator herein in view of its polymerized monomer and product molecular weight. The amount is 0.1 to 1.0%, preferably 0.2 to 0.6% based on the mass of the acrylate monomer.
The micelle chain segment structure insoluble in the hand-washing-free liquid system can use a chain transfer agent for effectively controlling the molecular weight of the acrylate structure in the polymerization process, wherein the chain transfer agent is selected from one or a combination of octyl mercaptan, n-dodecyl mercaptan, tert-dodecyl mercaptan, hexadecyl mercaptan, octadecyl mercaptan (ODM), isooctyl 3-mercaptopropionate (IMP), butyl 3-mercaptopropionate, 3-mercaptopropionic acid, butyl mercaptoacetate, isooctyl mercaptoacetate and dodecyl mercaptoacetate; n-dodecyl mercaptan is preferred as the chain transfer agent in the present invention. The amount of the catalyst is 0.01% -1%, preferably 0.05% -0.25% based on the mass of the acrylate monomer.
It is another object of the present invention to provide a method for preparing the thickener for leave-on hand sanitizer systems.
The preparation method of the thickener for the no-clean hand sanitizer system comprises the following steps:
a) After dehydrating polyether polyol, adding a catalyst and polyisocyanate into the polyether polyol in an inert gas environment, wherein the molar ratio of isocyanate to polyether polyol is 1.2:1-2.0:1, the adding amount of the catalyst is 0.08-0.12% based on the mass of isocyanate, starting a polymerization reaction, adding a compound containing hydroxyl and double bonds after reacting for 1-3 hours, and further polymerizing for 1-3 hours, wherein the adding amount of the compound containing hydroxyl and double bonds is 0.1-5.0 times based on the mass of isocyanate, so as to obtain a polymer solvated chain segment containing double bonds;
b) Under a certain temperature and inert gas environment, adding a solvent into a reaction container, simultaneously adding a polymer solvation chain segment containing double bonds, which accounts for 40-70% of the mass of the solvent, dropwise adding acrylic monomer styrene and/or methyl methacrylate or a mixture thereof into the solvent within a metering time of 1-3h, wherein the addition amount of the acrylic monomer styrene and/or methyl methacrylate is 30-60% of the mass of the solvent, adding a mixed component of a chain transfer agent and an initiator, performing free radical polymerization, and obtaining the thickener for thickening the wash-free liquid after 2-5h of reaction.
The synthesis of the double bond containing polymeric solvated segments in step a) of the present invention may be carried out by various methods for preparing polyurethane resins, the synthesis may be carried out in the absence of water, for example, in some embodiments azeotropic dehydration or vacuum heating dehydration may be employed; during the reaction, nitrogen is adopted for protection, so that water vapor is prevented from entering. The synthesis can be carried out by a solution method or a bulk synthesis method. The invention is preferably synthesized by a bulk method.
The thickener synthesized in step b) of the present invention for use in the leave-on hand wash system is polymerized by solvent method, the selection criteria of the solvent being that there are no active hydrogen groups reactive with isocyanate groups and that there are suitable melting points and boiling points, such solvents include, but are not limited to, benzene, toluene, xylene, ethylbenzene, chloroform, acetone, butyl acetate, or several combinations thereof; in view of environmental protection, butyl acetate is preferred here, the amount of which is 50-60% of the mass of the overall polymerization system comprising solvent, double bond-containing polymer solvated segment, acrylic monomer, initiator and chain transfer agent.
In some embodiments, the polymerization temperature of step a) and step b) of the present invention is not strictly limited, and the polymerization temperature may be selected to be 40-130 ℃, preferably 50-120 ℃, more preferably 70-110 ℃, so that the production of byproducts may be effectively reduced and the quality of the product may be improved.
In some embodiments, steps a) and b) of the present invention require protection with an inert gas, which is nitrogen and/or helium, preferably nitrogen.
In addition, the preparation step a) of the thickener for a leave-on hand lotion system according to the present invention is carried out under catalyst conditions, wherein the catalyst is one or more of an organometallic catalyst and/or an amine catalyst. Wherein the organic metal catalyst is one or more of dibutyl tin dilaurate, stannous octoate, bismuth caprate, bismuth octoate and silver catalysts; the amine catalyst is triethylamine and/or 1, 4-diazabicyclo [2.2.2] octane.
It is a further object of the present invention to provide the use of said thickener for leave-on hand wash systems.
The invention has the positive effects that:
the thickener for the no-clean hand sanitizer system adopts the basic principle that the polyurethane thickener thickens in the water phase, and polymerizes to obtain the micelle chain segment containing the solvation chain segment which can be freely stretched in the no-clean hand sanitizer system and the performance association structure, and can establish a three-dimensional net structure in a high-ethanol system through association coordination, so that the movement of free molecules in the system is restrained, the viscosity of a product is greatly improved, and the requirement of the viscosity of the no-clean hand sanitizer for use is met.
Detailed Description
The invention will be further illustrated with reference to the following examples, which are not intended to limit the invention in any way.
The commercial products polyurethane thickener B1 and powder carbomer B2 were selected as comparative examples and compared with the products of the following examples in different leave-on hand lotion formulations.
Wherein the polyurethane thickener B1 is selected to be DOW chemicalRM-8W, B1 is a traditional linear thickener, and is mainly polymerized by polyethylene glycol, polyisocyanate and blocked alkyl chain. The product has higher market acceptance, and the main parameters are as follows:
wherein the carbomer thickener B2 is Carbopol 480 NF, B2 is highly crosslinked polyacrylic acid. The product has higher market acceptance, and the main parameters are as follows:
| appearance of | White loose powder |
| Chemical type | Polyacrylic acid |
| Density of | 1.063g/cm3 |
| Containing carboxylic acid groups | 56-68％ |
| PH value (1% aqueous solution) | 2.5-3 |
The main monomer information is as follows:
screw extruder: nanj electro-mechanical limited, SHJ-20B.
GPC test instrument model: e2695-2414RID, volter.
Example 1
The thickener C1 for the no-clean hand sanitizer system is prepared, and the synthetic formula comprises the following components:
TABLE 1
The thickener for the no-clean hand sanitizer system synthesized by adopting the formula comprises the following steps:
1) 80g of polyethylene glycol 6000 (PEG 6000) is added into 500ml of a three-mouth bottle provided with electromagnetic stirring and a nitrogen inlet, negative pressure (pressure is less than 100 Pa) is adopted, and water is removed for 2 hours at 110 ℃;
2) Cooling to 80 ℃, introducing nitrogen into the three-neck flask for pressure relief, adding 0.0025g 8108R and 2.8g HDI into the three-neck flask, and starting the polymerization reaction for 2 hours;
3) Adding 0.8676g of hydroxyethyl methacrylate into a three-neck flask, maintaining the temperature at 80 ℃, polymerizing for 2 hours, cooling to 60-65 ℃ after the full reaction is completed, and standing for standby, thereby obtaining a double bond-containing polymer solvated chain segment, and obtaining a double bond-containing polymer solvated chain segment with the molecular weight Mw=25101;
4) Under nitrogen atmosphere, 71.25g of butyl acetate and 50g of the obtained polymer containing double bonds are added into a 500ml flask, stirring is started, the temperature is raised to 80 ℃,10 g of butyl acetate, 31.15g of styrene, 0.078g of BPO and 0.022g of dodecyl mercaptan are weighed in a dropping bottle and are uniformly mixed, liquid in the dropping bottle is dripped into the flask for polymerization reaction within 2 hours, and the dripping is completed, and the temperature is kept for 2 hours, so that the polymer for the hand washing-free liquid is obtained;
5) And (3) removing the excessive solvent from the polymer by using a screw extruder to obtain polymer solids. The obtained 81.2g of polymer solid was dissolved in 189.6g of water and cooled to room temperature to obtain thickener C1 for a leave-on hand sanitizer system.
The resulting C1 was tested by GPC molecular weight as mw= 40739.
Example 2
The thickener C2 for the no-clean hand sanitizer system is prepared, and the synthetic formula comprises the following components:
TABLE 2
The thickener for the no-clean hand sanitizer system synthesized by adopting the formula comprises the following steps:
1) 80g of polyethylene glycol 8000 (PEG 8000) was added to 500ml of a three-necked flask equipped with electromagnetic stirring and nitrogen inlet, under negative pressure (pressure less than 100 Pa), and dehydrated at 110℃for 2 hours;
2) Cooling to 80 ℃, introducing nitrogen into the three-neck flask for pressure relief, adding 0.0052g 8108R and 5.247g HMDI into the three-neck flask, and starting the polymerization reaction for 2 hours;
3) Adding 26.08g of polyethylene glycol acrylate-28 into a three-neck flask, maintaining the temperature at 80 ℃ for 2 hours, and standing for standby after the complete reaction is cooled to 60-65 ℃ to obtain a double bond-containing polymer solvated chain segment, wherein the molecular weight of the double bond-containing polymer solvated chain segment is Mw=11133;
4) Under nitrogen atmosphere, adding 35.4 butyl acetate and 18g of the obtained polymer solvated chain segment polymer containing double bonds into a 500ml flask, starting stirring and heating to 80 ℃, weighing 8g butyl acetate, 25.2g methyl methacrylate, 0.14g BPO and 0.055g dodecyl mercaptan in a dropping bottle, uniformly mixing, dropping the liquid in the dropping bottle into the flask for polymerization reaction within 2 hours, and preserving the heat for 2 hours after the dropping is completed, thus obtaining the polymer for the hand washing free liquid;
5) And (3) removing the excessive solvent from the polymer by using a screw extruder to obtain polymer solids. 43.4g of the obtained polymer solid was dissolved in 101.3g of water and cooled to room temperature to obtain thickener C2 for a leave-in hand sanitizer system.
The resulting C2 was tested by GPC molecular weight as mw=26733.
Example 3
The thickener C3 for the no-clean hand sanitizer system is prepared, and the synthetic formula comprises the following components:
TABLE 3 Table 3
The thickener for the no-clean hand sanitizer system synthesized by adopting the formula comprises the following steps:
1) 80g of polyethylene glycol 8000 (PEG 8000) was added to 500ml of a three-necked flask equipped with electromagnetic stirring and nitrogen inlet, under negative pressure (pressure less than 100 Pa), and dehydrated at 110℃for 2 hours;
2) Cooling to 80 ℃, introducing nitrogen into the three-neck flask for pressure relief, adding 0.003g 8108R and 2.523g HDI into the three-neck flask, and starting polymerization reaction for 2 hours;
3) Adding 2.985g of 9-alkenyl-12-hydroxyoctadecanoic acid into a three-neck flask, maintaining the temperature at 80 ℃, polymerizing for 2 hours, cooling to 60-65 ℃ after full reaction is completed, and standing for standby, thereby obtaining a double bond-containing polymer solvated chain segment, wherein the molecular weight of the double bond-containing polymer solvated chain segment is Mw=17102;
4) Under nitrogen atmosphere, adding 44.5g of butyl acetate and 25g of the obtained polymer solvated chain segment polymer containing double bonds into a 500ml flask, starting stirring and heating to 80 ℃, weighing 10g of butyl acetate, 29.4g of methyl methacrylate, 0.09g of BPO and 0.035g of dodecyl mercaptan in a dropwise adding bottle, uniformly mixing, dropwise adding the liquid in the dropwise adding bottle into the flask for polymerization reaction within 2 hours, and preserving the heat for 2 hours after dropwise adding, thus obtaining the polymer for the hand washing free liquid;
5) And (3) removing the excessive solvent from the polymer by using a screw extruder to obtain polymer solids. 54.5g of the obtained polymer solid was dissolved in 127.24g of water and cooled to room temperature to obtain thickener C3 for a leave-on hand sanitizer system.
The resulting C3 was tested by GPC molecular weight as mw= 37218.
Example 4
The thickener C4 for the no-clean hand sanitizer system is prepared, and the synthetic formula comprises the following components:
TABLE 4 Table 4
The thickener for the no-clean hand sanitizer system synthesized by adopting the formula comprises the following steps:
1) 80g of polyethylene glycol 4000 (PEG 4000) was added to 500ml of a three-necked flask equipped with electromagnetic stirring and nitrogen inlet, under negative pressure (pressure less than 100 Pa) and dehydrated at 110℃for 2 hours;
2) Cooling to 80 ℃, introducing nitrogen into the three-neck flask for pressure relief, adding 0.0070 g 8108R and 6.296g HMDI into the three-neck flask, and starting the polymerization reaction for 2 hours;
3) Adding 0.688g of hydroxyethyl acrylate into a three-neck flask, maintaining the temperature at 80 ℃ for 2 hours, and standing for standby after the full reaction is completed and the temperature is reduced to 60-65 ℃ to obtain a double bond-containing polymer solvated chain segment, wherein the molecular weight of the double bond-containing polymer solvated chain segment is Mw= 21746;
4) Under nitrogen atmosphere, adding 62.46g of butyl acetate and 50g of the obtained polymer containing double bonds and solvated chain segments into a 500ml flask, starting stirring and heating to 80 ℃, weighing 10g of butyl acetate, 22.35g of methyl methacrylate, 0.083g of BPO and 0.036g of dodecyl mercaptan in a dropwise adding bottle, uniformly mixing, dropwise adding the liquid in the dropwise adding bottle into the flask for polymerization reaction within 2 hours, and preserving the heat for 2 hours after dropwise adding, thus obtaining the polymer for the hand washing free liquid;
5) And (3) removing the excessive solvent from the polymer by using a screw extruder to obtain polymer solids. 72.5g of the polymer solid obtained was dissolved in 169.1g of water and cooled to room temperature, to obtain thickener C4 for a leave-in hand sanitizer system.
The resulting C4 was tested by GPC molecular weight as mw= 31465.
Example 5
The thickener C5 for the no-clean hand-washing liquid system is prepared, and the synthetic formula comprises the following components:
TABLE 5
The thickener for the no-clean hand sanitizer system synthesized by adopting the formula comprises the following steps:
1) 80g of polyethylene glycol 6000 (PEG 6000) is added into 500ml of a three-mouth bottle provided with electromagnetic stirring and a nitrogen inlet, negative pressure (pressure is less than 100 Pa) is adopted, and water is removed for 2 hours at 110 ℃;
2) Cooling to 80 ℃, introducing nitrogen into the three-neck flask for pressure relief, adding 0.003g 8108R and 2.99g HDI into the three-neck flask, and starting polymerization reaction for 2 hours;
3) Adding 0.89g of hydroxyethyl methacrylate into a three-neck flask, maintaining the temperature at 80 ℃ for 2 hours, and standing for standby after the complete reaction is cooled to 60-65 ℃ to obtain a double bond-containing polymer solvated chain segment, wherein the molecular weight of the double bond-containing polymer solvated chain segment is Mw= 18873;
4) Under nitrogen atmosphere, adding 65.8g of butyl acetate and 40g of the obtained polymer solvated chain segment polymer containing double bonds into a 500ml flask, starting stirring and heating to 80 ℃, weighing 10g of butyl acetate, 20.6g of styrene, 15g of methyl methacrylate, 0.15g of BPO and 0.07g of dodecyl mercaptan in a dropwise adding bottle, uniformly mixing, dropwise adding liquid in the dropwise adding bottle into the flask for polymerization reaction within 2 hours, and preserving heat for 2 hours after dropwise adding, thus obtaining the polymer for the hand washing free liquid;
5) And (3) removing the excessive solvent from the polymer by using a screw extruder to obtain polymer solids. 75.8g of the polymer solid obtained was dissolved in 176.9g of water and cooled to room temperature to obtain thickener C1 for a leave-in hand sanitizer system.
The resulting C5 was tested by GPC molecular weight as mw= 35667.
Examples 6-7 below are examples of application of the thickeners described above for leave-on hand sanitizer systems, as compared to commercially available thickeners B1, B2. The items and methods to be tested are as follows:
1) Thickening efficiency, namely adding the same metering thickener into a system, and examining the viscosity of the system at 20rpm and the unit cp;
2) Transparency test: measurement was performed using a You Nike 7200 spectrophotometer, with 100% optimal;
3) Storage stability, namely placing the prepared finished paint into a baking oven at 50 ℃ for 14 days, and examining the viscosity change of the hand-washing-free liquid soap; determination criteria: the storage stability is 5 minutes, and the storage stability is not 1 minute;example 6
The comparison of thickeners C1, C2, C3, C4, C5 for leave-on hand sanitizer systems synthesized in examples 1-5 of the invention with commercial products is shown at a relatively high ethanol content (about 75% by volume). Mixing the following materials.
TABLE 6
| Numbering device | Raw materials | Mass/g |
| 1 | Water and its preparation method | 29 |
| 2 | Ethanol | 70 |
| 3 | Thickening agent | 1 |
In this formulation, thickeners C1-C5 and commercial products B1, B2 for leave-on hand sanitizer systems synthesized in the comparative examples gave the following table results:
TABLE 7
| Test item | B1 | B2 | C1 | C2 | C3 | C4 | C5 |
| Viscosity of the mixture | 90 | 4000 | 4200 | 4120 | 4066 | 4287 | 4320 |
| Transparency of the film | 86％ | 92％ | 92％ | 94％ | 94％ | 94.5％ | 94.7％ |
| Storage stability | 5 | 4 | 5 | 5 | 5 | 5 | 5 |
As can be seen from Table 7, the thickener for a leave-on hand sanitizer system of the present invention has higher thickening efficiency in a high ethanol content system, and simultaneously has better transparency and storage stability. Can meet the performance requirement of the hand-washing-free liquid soap.
Example 7
In the common leave-on hand sanitizer formulations in the market, the synthetic thickeners C1, C2, C3, C4, C5 for the leave-on hand sanitizer system were added to compare with commercially available products.
The formula of the conventional no-clean hand cleanser is as follows:
TABLE 8
In this formulation, comparative examples synthesized thickeners C1-C5 and commercial products B1, B2 for leave-in hand wash systems, giving the following Table results:
TABLE 9
| Test item | B1 | B2 | C1 | C2 | C3 | C4 | C5 |
| Viscosity of the mixture | 75 | 3200 | 3400 | 3360 | 3266 | 3466 | 3522 |
| Transparency of the film | 76％ | 82％ | 83％ | 84％ | 84％ | 84％ | 84.2％ |
| Storage stability | 4 | 4 | 5 | 5 | 5 | 5 | 5 |
It can be seen from Table 9 that the thickener for leave-on hand-wash systems of the present invention also has better thickening efficiency in the conventional leave-on hand-wash formulations in the market, while not affecting transparency and storage stability.
The above embodiments are preferred embodiments of the present invention, but the present invention is not limited by the above embodiments, and any other changes, modifications, simplifications, substitutions made without departing from the spirit and principles of the present invention should be made in equivalent ways, and the invention is also within the scope of the present invention.
Claims (12)
1. A thickener for a leave-on hand sanitizer system, characterized in that the polymer main chain of the thickener comprises a solvation chain segment which is freely stretched in the leave-on hand sanitizer system and a micelle chain segment which is insoluble in the leave-on hand sanitizer system, the solvation chain segment and the micelle chain segment are connected through a compound structure containing hydroxyl groups and double bonds, and the thickener for the leave-on hand sanitizer system has the following structure:
wherein,
a is a residue of a polyisocyanate and,
b is a polyether polyol residue,
d is a compound residue containing hydroxyl and double bonds,
e is a micelle chain segment structure insoluble in a no-wash hand-washing liquid system,
m is any integer from 1 to 5; the compound containing hydroxyl and double bond related to the compound residue D containing hydroxyl and double bond is one or more of hydroxyethyl (methyl) acrylate, hydroxypropyl (methyl) acrylate, polyethylene glycol (methyl) acrylate and 9-alkenyl-12-hydroxyoctadecanoic acid; the micelle chain segment structure insoluble in the no-clean hand-washing liquid system is formed by polymerizing styrene and/or methyl methacrylate.
2. Thickener according to claim 1, wherein the polyisocyanate referred to by the polyisocyanate residue a is a di-and/or tri-isocyanate;
and/or the diisocyanate is one or more of aliphatic diisocyanate, alicyclic diisocyanate and aromatic diisocyanate;
and/or the triisocyanate is one or more of 4,4' triphenylmethane triisocyanate, 2-isocyanatoethyl 2, 6-diisocyanatohexanoate and HDI trimer.
3. The thickener according to claim 2, wherein the aliphatic diisocyanate is selected from one or more of 1, 6-hexamethylene diisocyanate, isophorone diisocyanate and dicyclohexylmethane diisocyanate; the aromatic diisocyanate is selected from toluene diisocyanate and/or 4, 4-diphenyl methane diisocyanate.
4. A thickener according to any of claims 1 to 3, wherein the polyether polyol referred to by polyether polyol residue B is one or more of polyethylene glycol, polypropylene glycol, polyethylene glycol-polypropylene glycol and polytetramethylene glycol;
and/or the polyether polyol has a molecular weight of 2000-20000 daltons.
5. The thickener according to claim 4, wherein the molecular weight is 4000 to 8000 daltons
6. A thickener according to any of claims 1 to 3, wherein said micelle segment structure of the leave-on liquid soap-insoluble system has a molecular weight of 200 to 15000 daltons.
7. The thickener according to claim 6, wherein the micelle segment structure of the non-wash-free hand sanitizer system has a molecular weight of 4000 to 11000 daltons.
8. A method of preparing a thickener according to any of claims 1 to 7, comprising the steps of:
a) Carrying out a polymerization reaction on polyether polyol and polyisocyanate after dehydration treatment, and adding a compound containing hydroxyl and double bonds for a certain time to carry out a polymerization reaction to obtain a polymer solvated chain segment containing double bonds;
b) And under the nitrogen environment, adding a polymer solvation chain segment containing double bonds into a solvent, adding styrene and/or methyl methacrylate, and performing free radical polymerization to obtain the thickener for thickening the wash-free liquid soap after the reaction is completed.
9. The process of claim 8 wherein step a) the molar ratio of isocyanate to polyether polyol is from 1.2:1 to 2.0:1; and/or the addition of the compound containing hydroxyl groups and double bonds is 0.1 to 5.0 times based on the mass of isocyanate; and/or, the polyether polyol and the polyisocyanate are subjected to polymerization reaction for 1-3 hours, and then the compound containing hydroxyl and double bonds is added for polymerization reaction for 1-3 hours.
10. The process according to claim 8 or 9, wherein in step a), the solvent is a solvent free of active H, including one or more of benzene, toluene, xylene, ethylbenzene, chloroform, acetone, butyl acetate; and/or adding a polymer solvating chain segment containing double bonds, wherein the polymer solvating chain segment accounts for 40-70% of the mass of the solvent, and the adding amount of the styrene and/or methyl methacrylate is 30-60% of the mass of the solvent.
11. Use of a thickener according to any of claims 1 to 7 or a thickener prepared by a process according to any of claims 8 to 10 in a thickener for leave-in hand wash systems.
12. Use of a thickener according to any of claims 1 to 7 or a thickener prepared by a process according to any of claims 8 to 10 in a thickener for leave-in hand wash of high ethanol content systems.
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