CN102153690B - Alternating or random copolymer containing polyquaternium lateral group and preparation method thereof - Google Patents
Alternating or random copolymer containing polyquaternium lateral group and preparation method thereof Download PDFInfo
- Publication number
- CN102153690B CN102153690B CN 201010597385 CN201010597385A CN102153690B CN 102153690 B CN102153690 B CN 102153690B CN 201010597385 CN201010597385 CN 201010597385 CN 201010597385 A CN201010597385 A CN 201010597385A CN 102153690 B CN102153690 B CN 102153690B
- Authority
- CN
- China
- Prior art keywords
- reaction
- group
- multipolymer
- trimethylamine
- olefin
- 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.)
- Active
Links
Landscapes
- Cosmetics (AREA)
- Detergent Compositions (AREA)
Abstract
The invention relates to an alternating or random copolymer containing a polyquaternium lateral group as well as a preparation method and an application method thereof. The preparation method comprises the following steps of: (1) generating an alternating or random copolymer containing a carboxylic acid anhydride group by copolymerization reaction of alpha-olefin and unsaturated diacid anhydride; (2) performing imidization reaction or esterification reaction on the obtained copolymer and organic tertiary amine containing a primary amine group or hydroxy to obtain a derivation containing a tertiary amine group; and (3) performing quaternization reaction on the polymer containing the tertiary amine group and an alkylation reagent to obtain the alternating or random copolymer containing the polyquaternium lateral group. The alternating or random copolymer containing the polyquaternium lateral group is a water-soluble polymer, has a good conditioning function on hair and skin, particularly endows the hair with good flexibility and conditioning property, is easily rinsed and is not accumulated; and the polymer can be used as a conditioning agent and a softening agent and can also be used as a retention and filtration aid and a reinforcing agent in the field of papermaking.
Description
Technical field
the present invention relates to a kind of water-soluble high-molecular compound and preparation method thereof, specifically a kind of contain the polyquaternium side group alternately or random copolymers and preparation method thereof, the electric density of this polymkeric substance is high, charge distribution is even, show conditioning performance and the anti-deposition properties of the not available excellence of traditional polyquaternium when using as amendment in skin care and hair products, this polymkeric substance also shows excellent compound property simultaneously, can not only be composite with positively charged ion and amphoterics, can also with the composite use of anion surfactant, this polymkeric substance also can be applicable to papermaking in addition, water treatment, the fields such as printing and dyeing and fabric treating.
Background technology
In hair washing, hair products, hair care, conditioning functions are the first elements of product performance.People's hair is made of Keratin sulfate, due to its poor electric conductivity, is subject to External Force Acting and produces static, destroys the overall look and feel of hair, makes hairs break, jag, also easily adsorbs black dirt simultaneously.So in order to keep the attractive in appearance and healthy of hair, change the hair quality surface charge and distribute, giving hair surface formation one deck protection matrix is ideal means.In cosmetic material, many products all have certain hair conditioning function.As various surfactants, organo-siloxane etc.But in this numerous product, what performance was the most excellent is the polymerizing cationically tensio-active agent.Polymerizing cationically can with shampoo in anion surfactant composite and do not produce precipitation, and can be adsorbed on the hair quality surface, eliminate electrostatic field and play the function of protection, conditioning hair.
But at present general polymerizing cationically accumulation phenomena on hair is serious, easy cleaning not, life-time service can make hair heavy, harden, affect the attractive in appearance of hair.Patent CN200610122572.2 has told about a kind of synthetic method of quaternised hydroxyethyl ether cellulose, but this product positively charged ion substitution value is low, thereby the product positive charge density is little, hair washing, in hair products conditioning functions a little less than, the hair loft after use is inadequate.Patent US5338541 has told about a kind of vinylformic acid/dimethyl diallyl ammonium chloride/acrylamide copolymer polyquaternium, this product positively charged ion substitution value is high, positive charge density is large, in hair washing, hair products, conditioning functions is preferably arranged, but this product easily gathers on hair, be difficult for rinsing, the life-time service hair can harden, and affects the aesthetic feeling of hair.
Summary of the invention
The present invention relates to a kind of contain the quaternary ammonium salt side group alternately or random copolymers and preparation method thereof.It is take alpha-olefin and unsaturated dibasic acid as comonomer, be quaternary ammonium group by the trimethylamine that contains primary amine group or hydroxyl, obtain through polyreaction, amidate action, quaterisation a kind of novel contain the polyquaternium side group alternately or random copolymers.
Specifically, according to a first aspect of the invention, the invention provides and contain replacing or random copolymers of quaternary ammonium salt side group, its main chain is the random copolymers of alpha-olefin and unsaturated dicarboxylic anhydride, described contain the quaternary ammonium salt side group alternately or random copolymers have two or more in following structural unit, wherein contain at least two kinds of structural units of A and B:
Wherein:
R and R
5Be C independently of one another
2～C
10The straight or branched alkylidene group, preferred C
2-C
8Alkylidene group, more preferably C
2-C
6Alkylidene group, more more preferably C
2-C
4Alkylidene group;
R
1, R
2And R
3Can be identical or different, be C independently of one another
1～C
6Alkyl, C
2～C
6Alkenyl or C
6～C
8Aralkyl; Preferably, be independently of one another C
1～C
3Alkyl, C
2～C
4Alkenyl or phenyl or benzyl; More preferably, be independently of one another methyl, ethyl, propyl group, sec.-propyl, normal-butyl, isobutyl-, sec-butyl, n-pentyl, isopentyl, sec.-amyl sec-pentyl secondary amyl, n-hexyl, isohexyl, Sec-Hexyl, phenyl or benzyl; These groups are unsubstituted or are replaced by hydroxyl or amino;
R
4Be C
4～C
20Alkyl or C
6～C
20Aralkyl, preferably C
4～C
12Alkyl or C
6～C
10Aralkyl; Be more preferably C
4～C
8Alkyl or C
6～C
8Aralkyl;
M is unsaturated dicarboxylic anhydride residue;
A
-Be one or more in halide-ions, sulfate group or carbonate group; Preferably, A
-Halogen, sulfate group R
3OSO
3 -Or carbonic ether R
3OCO
2 -In one or more; More preferably CH
3OSO
3 -, CH
3CH
2OSO
3 -, Cl
-, Br
-, I
-, CH
3-O-C (=O) O
-Or CH
3-CH
2-O-C (=O) O
-In one or more;
Carboxyl in D, E and F structural unit can be not neutralize, and can be also part neutralization or all neutralizations.
Preferably, this multipolymer comprises: 1) the structural unit A of 45～60mol%; 2) structural unit B and/or the E of 20～55mol%; 3) the structural unit C of 〉=0mol%～10mol%; 4) the structural unit D of 〉=0mol%～10mol%, these percentage ratios are based on the total mole number of the entire infrastructure unit in copolymer skeleton.
This product is used as amendment in shampoo, hair conditioner, compound property is good, has the hair soft of making, fluffy effect, easily rinsing, and good hand touch, the hair after washing is smooth, beautiful, and easily combing has moisture-keeping functions.It has the polyquaternium compound of present use and the function of cation opsonizing agent concurrently, and the hairdressing ability is strong, but can not produce storage effect, is multifunctional hair cleaning of new generation, hair conditioner.
According to a second aspect of the invention, provide the method for the above-mentioned multipolymer of preparation, it comprises the following steps:
Steps A), copolymerization
Alpha-olefin and unsaturated dicarboxylic anhydride carry out alternating polymerization or random copolymerization to prepare random or alternating copolymer prepares skeleton or main chain
In the past, we adopt the solvent deposition polymerization to carry out the Synthesis of copolymer of alpha-olefin and unsaturated dicarboxylic anhydride under normal conditions, its principle be with alpha-olefin and unsaturated dicarboxylic anhydride solvent in a kind of special solvent, copolyreaction occurs under the effect of initiator, the polymkeric substance that generates can obtain powder-like product due to insoluble being precipitated out in reaction solvent through centrifugation (or filtration) and drying after polymerization is completed.When adopting solvent polymerization method, reaction is carried out in the good solvent of a kind of polymkeric substance and monomer in addition, the polymers soln that at last reaction is obtained carries out precipitate and separate and drying in precipitation agent, thereby obtains solid product.
The advantage of solvent polymerization method is that polyreaction can be controlled at a lower temperature and carries out, and the purity of the product that obtains is higher, but its shortcoming is: 1) generally below 40%, plant factor is low for the solid content of polyreaction; 2) a large amount of solvent losses is arranged, production cost is high; What 3) use is the organic solvent with certain hazardness, has environmental risk and worker health risk.
In the present invention, what alpha-olefin involved in the present invention and the Synthesis of copolymer of unsaturated dicarboxylic anhydride adopted is mass polymerization, can effectively control the above-mentioned shortcoming of solvent polymerization method, and plant factor is high, and there is no the risk of environmental protection aspect.The flow process of this polymerization process is: alpha-olefin and unsaturated dicarboxylic anhydride are added in reactor, be heated to 130～220 ℃ and carry out polyreaction under nitrogen protection, temperature of reaction preferably is controlled at 120～200 ℃, 150～180 ℃ of optimal reaction temperatures.Polymeric reaction temperature is during lower than 130 ℃, owing to being separated and the problem of efficiency of initiation, can cause rate of polymerization to reduce, and transformation efficiency reduces.Polymeric reaction temperature is during higher than 220 ℃, and polymericular weight is low, and molecular weight distribution is too wide.This reaction can be adopted thermal initiation or initiator initiated polymerization, uses initiator can accelerate polymerization rate.Can add molecular weight regulator in polymerization process, carry out the molecular weight of polymkeric substance and the regulation and control of molecular weight distribution, in order to make the molecular structure of polymkeric substance more even, more regular.After completing, polyreaction removes unreacted monomer and other low molecular compound by underpressure distillation.Gained alpha-olefin and unsaturated dicarboxylic anhydride alternately or the number-average molecular weight of random copolymers be 2500～300000.
In a broad sense, the alpha-olefin of reaction use is CH
2=CHR
4, R wherein
4Be C
4～C
20Alkyl or C
6～C
20Aralkyl, preferably C
4～C
12Alkyl or C
6～C
10Aralkyl;
Preferred CH
2=CHR
4C
6～C
22The normal olefine class is as 1-hexene, 1-octene, 1-decene, 1-laurylene, 1-tetradecylene, 1-hexadecylene, 1-octadecylene, 1-icosa alkene or 1-docosene etc.; Or C
6～C
22The branched-chain alkene class is as 1-methylpentene, 1-methyl heptene, 1-methyl nonene, 1-methyl hendecene-1, methyl tridecylene-1, methyl ten pentaenes-1, methyl 17 alkene-1, methyl 19 alkene-1 or methyl two hendecenes-1 etc.; Or C
8～C
22Vinyl aromatic (co) hydro carbons (as vinylbenzene) or C
1-C
3The vinyl aromatic (co) hydro carbons that alkyl replaces; Or the mixture of two or more above-mentioned alpha-olefins; More preferably CH
2=CHR
4C
10～C
22Straightαolefin.
Unsaturated dicarboxylic anhydride in the present invention is the one or two or more in maleic anhydride, methyl-maleic acid acid anhydride, laurylene Succinic anhydried and Tetra Hydro Phthalic Anhydride.
in polyreaction, the feed ratio of alpha-olefin and unsaturated dicarboxylic anhydride can be different with the difference of the structure of the multipolymer that needs to control because of the kind of unsaturated dicarboxylic anhydride, for example 1-hexadecylene or vinylbenzene and maleic anhydride reaction, the product overwhelming majority is for having the alternating copolymer of ordered structure, therefore generally take equimolar ratio to feed intake, or wherein a kind of comonomer is slightly excessive, as 5～10mol%, and when one or more in comonomer have the tendency of larger random copolymerization, can carry out according to the requirement of molecular designing the design of feed ratio, general usage ratio can be alpha-olefin: unsaturated dicarboxylic anhydride=1.0: 0.5～1.1 (mol ratio).If when in polyreaction, the feed ratio of alpha-olefin and unsaturated dicarboxylic anhydride was higher than 1.0: 0.5 (mol ratio), the polymer cation substitution value of generation was low, the conditioning of product is poor.If when in polyreaction, the feed ratio of alpha-olefin and unsaturated dicarboxylic anhydride was lower than 1.0: 1.1 (mol ratio), the polymer cation substitution value of generation was too high, cause product cumulative bad on hair to increase, make the hair hardening, be difficult to combing.
Generally prepare multipolymer with the alpha-olefin of 45～60mol% and the unsaturated dicarboxylic anhydride of 40～55mol%, based on the total mole number of two kinds of monomers.
The initiator that uses for the acceleration polyreaction can be: hydroperoxide, as isopropyl benzene hydroperoxide and tertbutyl peroxide etc.; Or peroxidation two acyls, as benzoyl peroxide and peroxidation two different nonanoyls etc.; Or the peroxidation dioxane, as dicumyl peroxide and di-t-butyl peroxide etc.; Or the peroxy dicarbonate compound, as percarbonic acid two (4-tertiary butyl cyclohexyl), percarbonic acid diisopropyl ester, percarbonic acid di-secondary butyl ester and percarbonic acid two (2-ethylhexyl) etc., or the mixture of above-mentioned initiator.In polyreaction, the add-on of initiator is 0.01～0.15% (weight ratio) of polymerization single polymerization monomer gross weight, best initiator add-on is 0.03～0.13% (weight ratio) of polymerization single polymerization monomer gross weight, and best initiator add-on is the 0.05-0.08% (weight ratio) of polymerization single polymerization monomer gross weight.When the consumption of initiator during less than 0.01% (weight ratio), it is not obvious that polyreaction is accelerated, and during greater than 0.15% (weight ratio), in polyreaction, the polymerization activity center is too many when the consumption of initiator, the thing molecular weight that causes getting together is low, and reaction is easily out of control.
Can also use chain-transfer agent to carry out the control of molecular weight and molecualr weight distribution in reaction, what can be used as that chain-transfer agent uses has Dodecyl Mercaptan, the positive Dodecyl Mercaptan ester of acetic acid and an isopropyl xanthogen disulfide etc., preferred Dodecyl Mercaptan, add-on is 0.01%～1% (weight percent) of polymerization single polymerization monomer gross weight.This step obtains replacing of alpha-olefin and unsaturated dicarboxylic anhydride or random copolymers (being called for short copolymer 1 or polymkeric substance 1).
Step B) imidization reaction or esterification
Imidization reaction:
Above steps A) anhydride group in the multipolymer (being copolymer 1) that obtains can with the trimethylamine H that contains primary amine groups
2N-R-NR
1R
2Compound generation amidate action, and can generate imide group by the dehydration reaction of carboxyl and amide group, for explaining conveniently, this two-step reaction is referred to as imidization reaction.Namely can introduce tertiary amine group in polymkeric substance by copolymer 1 and the trimethylamine generation imidization reaction that contains primary amine group, obtain the multipolymer (being called for short multipolymer 2) of imidization.
In general concrete building-up process is: polymkeric substance 1 (alpha-olefin replaces or random copolymers with unsaturated dicarboxylic anhydride) is mixed with polyethers (polyethers of preferred low-molecular-weight C1-C6 low alkyl group end-blocking) as reaction solvent, then add the trimethylamine H that contains primary amine groups
2N-R-NR
1R
2, be heated to 60～200 ℃ (preferred 100～200 ℃, more preferably 120～180 ℃, most preferably 140～160 ℃) and carry out imidization reaction.After completing, imidization reaction can eliminate unreacted low molecular compound by underpressure distillation.In acylation reaction in copolymer 1 the ratio of the total mole number of acid anhydrides unit and trimethylamine mole number be 1.0: 0.6～1.0: 1.2, optimum proportion is 1.0: 0.8～1.0: 1.0;
Or esterification:
Anhydride group in copolymer 1 can with the trimethylamine HO-R of hydroxyl
5-NR
1R
2Carry out esterification, namely can be by the trimethylamine HO-R of polymkeric substance 1 with hydroxyl
5-NR
1R
2Carry out esterification, introduce tertiary amine group in polymkeric substance, obtain esterified copolymer (being called for short multipolymer 3).Preferably, esterification can be carried out at relatively low temperature.
In general concrete synthetic method is: copolymer 1 (alpha-olefin replaces or random copolymers with unsaturated dicarboxylic anhydride) is mixed with polyethers (polyethers of preferred low-molecular-weight C1-C6 low alkyl group end-blocking) as reaction solvent, then add the trimethylamine HO-R of hydroxyl
5-NR
1R
2, be heated to 60～200 ℃ (preferred 60～150 ℃, more preferably 70～140 ℃, most preferably 80～120 ℃) and carry out esterification.Reaction can be eliminated unreacted low molecular compound by underpressure distillation after finishing.In esterification in polymkeric substance 1 ratio of the total mole number of acid anhydrides unit and trimethylamine mole number be 1.0: 0.6～1.0: 1.2, optimum proportion is 1.0: 0.8～1.0: 1.0.
Step C), quaterisation
Product---the multipolymer 2 that imidization reaction is obtained; after or the product that obtains of esterification---multipolymer 3 mixes with alkylating reagent, be heated to 70～150 ℃ and carry out quaterisation and obtain the polyquaternium cation compound under the nitrogen protection condition.Preferred this temperature of reaction is at 80～140 ℃, more preferably 90～130 ℃, and optimal reaction temperature 100-115 ℃.The polymkeric substance 2 of participation reaction or the mole number of the tertiary amine group in polymkeric substance 3 are 1.0: 0.5～1.0: 1.0 with the ratio of the mole number of the alkylating reagent of participating in reaction, preferred 1.0: 0.6～1.0: 1.0, and most preferably 1.0: 0.8～1.0: 1.0.Cool to 45-85 ℃ after reaction, add appropriate amount of deionized water to obtain a kind of polyquaternium aqueous products with certain viscosity, according to the difference of solid content, product can present flow-like or paste body shape.Have the viscosity of 80～182mPas when this product with deionized water is diluted to the aqueous solution of 10% solid content, dried polymkeric substance has the nitrogen content of 2.27-6.16wt%.
Preferably to contain the total carbon atom number of primary amine group be 4～12 trimethylamine H to imidization reagent in the present invention
2N-R-NR
1R
2More preferably, it is selected from N, N-dimethyl-1，2-diaminoethane, N, and N-dimethyl-1,3-propylene diamine and N, the one or two or more in the N-dimethyl-p-phenylenediamine, more preferably it is N, N-dimethyl-1,3-propylene diamine or N, N-dimethyl-1，2-diaminoethane.
Preferably to contain the total carbon atom number of hydroxyl be 4～12 trimethylamine HO-R to esterifying reagent in the present invention
5-NR
1R
2More preferably it is selected from N, N-dimethylisopro panolamine, N, N-dimethylethanolamine, N, N-dimethyl propanol amine, trolamine, tri-isopropanolamine, to hydroxyl N, accelerine and 3-dimethylin-1, one or two or more in the 2-propylene glycol is more preferably N, the N-dimethyl propanol amine.
In the present invention the alkylating reagent that uses of alkylated reaction preferably, R
3A, wherein A is halogen Cl, Br or I, and R
3C
1-C
6Alkyl, C
2-C
6Thiazolinyl or C
6-C
8Aralkyl, or wherein A is sulfate group R
3OSO
3-or carbonic ether R
3OCO
2-, i.e. R
3A is sulfuric ester R
3OSO
3-R
3Or carbonic ether R
3OCO
2-R
3, two R wherein
3C independently of one another
1-C
6Alkyl, C
2-C
6Thiazolinyl or C
6-C
8Aralkyl.Preferably, this alkylating agent R
3A is that halohydrocarbon is (preferred, methyl chloride, monochloroethane, chlorobutane, Benzene Chloride, Benzyl Chloride etc.), or organo-sulfate or carbonate products are (preferred, methyl-sulfate, sulfuric acid methyl ethyl ester, ethyl sulfate, dibutyl sulfate, methylcarbonate, diethyl carbonate, Methyl ethyl carbonate etc., more preferably methyl-sulfate).
If at above step B) in use the trimethylamine H contain primary amine groups
2N-R-NR
1R
2Trimethylamine HO-R with hydroxyl
5-NR
1R
2Mixture replace containing the trimethylamine H of primary amine groups
2N-R-NR
1R
2Or the trimethylamine HO-R of hydroxyl
5-NR
1R
2, carry out simultaneously imidization and esterification, and at step B) in the total mole number and the trimethylamine C that contains primary amine group of acid anhydrides unit in polymkeric substance 1
2～C
10With the C that contains hydroxyl
2～C
10The ratio of the sum of both mole numbers of trimethylamine is 1.0: 0.6～1.0: 1.2, and optimum proportion is 1.0: 0.8～1.0: 1.0.
The polyethers of the low-molecular-weight C1-C6 low alkyl group end-blocking that uses in the present invention preferably has the polyethers of the low alkyl group end-blocking of following formula:
R’-O-(CH
2CH
2-O)n-(CH
2CHCH
3)m-R”，
Wherein R ' and R " can be C identical or different and independently of one another
1-C
6Alkyl (preferable methyl or ethyl or propyl group), n are that 2-25 and m are 0-15, and the n+m sum is between 2-25.Preferably, n is that 3-20 and m are 0-10, and the n+m sum is between 3-20.More preferably, n is that 3-20 and m are 0-5, and the n+m sum is between 3-20.
The number-average molecular weight of the polyethers of above-mentioned low-molecular-weight low alkyl group end-blocking is between 134-1000, preferably between 160-500.
The number-average molecular weight of polyquaternium compound of the present invention is generally 2550～350000, is preferably 5000～250000, and more preferably 10000～200000, more more preferably 20000～90000, most preferably 30000～80000.
In preferred embodiments, provide contain the quaternary ammonium salt side group alternately or the preparation method of random copolymers, it comprises the following steps:
A) alpha-olefin and unsaturated dicarboxylic anhydride are joined in reactor, temperature of reaction is controlled at 130～220 ℃, reacts after 7～24 hours, is replaced or random copolymers;
B) with steps A) multipolymer that obtains of polymerization joins in polyethers as reaction solvent, stir, add the trimethylamine that contains primary amine group, control 60～200 ℃ of temperature of reaction (preferred 100～200 ℃, more preferably 120～180 ℃, most preferably 140～160 ℃), reacted 2～9 hours (preferred 3～9 hours, more preferably 3～6 hours), and remove the water that dereaction produces, make part or all of maleic anhydride unit generation imidization reaction; Or with steps A) multipolymer that obtains of polymerization joins in polyethers as reaction solvent, stir, add the trimethylamine that contains hydroxyl, control 60～200 ℃ (preferred 60～150 ℃ of temperature of reaction, more preferably 70～140 ℃, most preferably 80～120 ℃), reacted 2～9 hours (preferred 2～8 hours, more preferably 3～6 hours), make part or all of maleic anhydride unit generation single-esterification;
C) at step B) add quaternizing agent in the multipolymer that contains tertiary amine group that obtains of reaction, make part or all of tertiary amine group carry out quaterisation, control 70～150 ℃ of temperature of reaction, randomly, add a certain amount of deionized water to be adjusted to required solid content after reaction, randomly, carry out the adjusting of pH value with alkaline matter.
Here " containing replacing or random copolymers of quaternary ammonium salt side group " is used interchangeably with " polyquaternium cation compound " or " polyquaternium compound ".
" quaternizing agent " is used interchangeably with " alkylating agent " in the present invention.
According to a third aspect of the present invention, provide contain the quaternary ammonium salt side group alternately or random copolymers as the purposes of amendment, softening agent and membrane-forming agent in personal-care supplies (as hair washing or hair products), makeup (as skin protection cosmetics) or common cleaning product.
Involved in the present invention contain the quaternary ammonium salt side group alternately or random copolymers skin, hair are had good opsonization, its performance is better than using in the market Polyquaternium-10 (polyquaternium-10).Its preparation process can be summarized as: the first step is to carry out the copolyreaction generation with straight or branched alpha-olefin and unsaturated dicarboxylic anhydride to contain replacing or random copolymers of anhydride group; Second step is that the polymkeric substance that contains acid anhydrides and binary organic amine (containing respectively a primary amine and a tertiary amine) that the first step reaction generates are carried out imidization reaction, obtain a kind of inferior amidation derivative that contains tertiary amine group, or allow the polymkeric substance that contains acid anhydrides and the hydroxyl tertiary amine of the first step reaction generation carry out esterification, generate the esterified derivative that contains tertiary amine group; The 3rd step was that the tertiary amine group that alkylating reagent and second step react in the polymkeric substance that generates carries out quaterisation, obtained containing replacing or random copolymers of quaternary ammonium salt side group.
Of the present invention contain the polyquaternium side group alternately or random copolymers skin, hair are had good conditioning, moisture-keeping functions, can not produce storage effect, be easy to rinsing, with various tensio-active agents, good compound property is arranged.Result of use is better than now widely used Polyquaternium-10 (polyquaternium-10) in skin care, hair washing, hair care articles.And synthesis technique is simple, and raw material consumption is reasonable, and cost is relatively low, save energy.
Of the present invention contain the quaternary ammonium salt side group alternately or random copolymers in personal-care supplies (as hair washing or hair products), makeup or cleaning product as the purposes of amendment, softening agent and membrane-forming agent, this polymkeric substance also can be applicable to the fields such as papermaking, water treatment, printing and dyeing and fabric treating in addition.
Embodiment
Product detects
1) viscosity: add 400g sample (being mixed with in advance 10% solid content) in the 500ml beaker, constant temperature to 25 ℃ uses the Brookfield-RVT viscometer, No. 1 rotor, 20 rev/mins of rotating speeds.The results are shown in Table 2 for the viscosity test of the product of all embodiment.
2) nitrogen content: the nitrogen content that uses the Kjeldahl determination testing product.The nitrogen content test result is listed in table 2.Application performance detects
Synthetic polyquaternium cation compound is made with following raw material and is carried out application performance after the shampoo product and detect:
Above-mentioned polyquaternium cation compound 0.3g; add EDTA-disodium (Guangzhou chemical reagent work) 0.05g; fatty alcohol-ether ammonium sulfate (Zhejiang is lucky to be reached) 16g; alkyl monoethanol amide (German section is peaceful) 2g; cocoyl CAB (Guangzhou be bestowed by heaven company) 5g; DMDMH sanitas (being bestowed by heaven in Guangzhou) 0.3g; citric acid (Gansu Province, west, Shantou) appropriate (0.2g); sodium-chlor (Guangdong salt industry) appropriate (0.2g); add deionized water to the 100g total amount, mix.The gained shampoo carries out viscosity, foam power, and transparence detects, and the human body evaluation contrast of the experiment of having one's hair wash.
1) viscosimetric analysis: add the 400g sample in the 500ml beaker, constant temperature to 25 ℃ uses the Brookfield-RVT viscometer, No. 3 rotors, 20 rev/mins of rotating speeds.
2) mensuration of foam power:
A) instrument and reagent: super thermostat, Luo Shi Latherometer, quantitative funnel (200ml), thermometer (0.1 ℃ of precision), beaker (800ml), calcium chloride (AR level), sal epsom (AR level).
B) determination step
A) preparation hard water (150mg/Kg): take MgSO
40.74g, CaCl
20.99g, be dissolved in appropriate water, transfer in the volumetric flask of 1000ml, be diluted with water to scale, shake up;
B) claim sample 1.0g (being accurate to 0.001g), add hard water 40ml, add deionized water 360ml, stir evenly constant temperature (40 ± 1) ℃;
C) get this liquid with quantitative funnel and rinse in a small amount Luo Shi Latherometer inwall, then get this liquid and put into the Luo Shi Latherometer, regulating liquid surface is to 50mm groove place;
D) get this liquid 200ml and vertically put on the good Luo Shi Latherometer of prior constant temperature, open the piston of quantitative funnel, allow under this liquid vertical current, the height that adds rear its foam of survey is its foaming power.
3) mensuration of transparence: adopt ultraviolet-visible spectrophotometer (UV-1700) working sample at the transmittance at 420nm place.
Embodiment 1
A) add 98.5g 1-laurylene and 70.1g maleic anhydride in the 1000ml four-hole glass reaction flask with stirring, thermometer, nitrogen tube, reflux condensing tube and heating unit etc., open and stir, logical nitrogen, open heating system after 30min, the temperature of reaction body fluid was warmed up to 155 ℃ from room temperature, isothermal reaction 14 hours reposefully in 1.0～1.5 hours.Connect vacuum pump after reaction finishes, reaction flask is vacuumized, remove unreacted material, obtain 1-octene/copolymer-maleic anhydride (copolymer 1), but cooling discharge or directly carry out next step reaction after reaction finishes.
B) add the 199.0g tetraethyleneglycol dimethyl ether in the copolymer 1 that the A reaction generates; stir; add 73.0g N; N-dimethyl-1, the 3-propylene diamine stirs; be warmed up to 160 ℃ under nitrogen protection; reacted 6 hours, and obtained the imide product (multipolymer 2) of copolymer 1, but cooling discharge or directly carry out next step reaction after reaction finishes.
C) add the 90.2g methyl-sulfate in the product of B reaction, stir, be warmed up to 110 ℃ under nitrogen protection, back flow reaction 6 hours slowly reduces the temperature to room temperature.Add the 270.0g deionized water in flask, stir the final product (polyquaternium compound) that forms white or faint yellow thickness paste form.
Adopt GPC, as reference, the number-average molecular weight that records the polyquaternium compound is 62600 with the sodium polyacrylate standard substance.
Embodiment 2～6
Repeat embodiment 1, just embodiment 1 each reactive material add-on is adjusted, as shown in table 1 below (unit, g)
Table 1
Embodiment 7
Repeat embodiment 1, just change the 1-laurylene that uses in the A reaction into the 1-icosa alkene, add-on is 164.1g, and the consumption of maleic anhydride is adjusted into the 57.8g temperature of reaction and is adjusted to 165 ℃.With the N that uses in the B reaction, N-dimethyl 1.3-propylene diamine changes N into, N-dimethyl 1.2-quadrol, and add-on is 46.4g.The consumption of methyl-sulfate in the C reaction is adjusted into 62.0g, and the consumption of deionized water is adjusted into 273.0g, 140 ℃ of temperature of reaction.After reaction is completed, synthetic polyquaternium cation compound is carried out the various detections identical with embodiment 1.
Embodiment 8
Repeat embodiment 1, just use tertbutyl peroxide to be initiator, add-on 0.097g in polyreaction.150 ℃ of A temperature of reaction, 7 hours reaction times.160 ℃ of B temperature of reaction, 6 hours reaction times.110 ℃ of C temperature of reaction, 6 hours reaction times.After reaction is completed, synthetic polyquaternium cation compound is carried out the various detections identical with embodiment 1.
Embodiment 9
Repeat embodiment 1, just use Dodecyl Mercaptan to be chain-transfer agent, add-on 0.019g in polyreaction.175 ℃ of A temperature of reaction, 7 hours reaction times.160 ℃ of B temperature of reaction, 6 hours reaction times.105 ℃ of C temperature of reaction, 6 hours reaction times.After reaction is completed, synthetic polyquaternium cation compound is carried out the various detections identical with embodiment 1.
Embodiment 10
Repeat embodiment 1, just change the 1-laurylene that uses in the A reaction into 1-tetradecylene, add-on is 112.0g, and the consumption of maleic anhydride is adjusted into 56.0g.With the N of the use in the B reaction, N-dimethyl-1, the 3-propylene diamine changes N into, the N-dimethyl propanol amine, add-on is 53.0g, temperature of reaction is 90 ℃.The consumption of methyl-sulfate in the C reaction is adjusted to 60.4g, and the consumption of tetraethyleneglycol dimethyl ether is adjusted into 169.0g, and the consumption of deionized water is adjusted into 230.0g.
Embodiment 11
Repeat embodiment 10, just change the 1-laurylene that uses in the A reaction into the 1-hexadecylene, add-on is 128.0g.With the N that uses in the B reaction, the add-on of N-dimethyl propanol amine is adjusted into 26.5g, and adds N, N-dimethyl-1, and the 3-propylene diamine, add-on is 26.2g, temperature of reaction is 120 ℃.The consumption of the tetraethyleneglycol dimethyl ether of use in the C reaction is adjusted into 162.0g, and the consumption of deionized water is adjusted into 206.0g.
Embodiment 12
Repeat embodiment 1, deionized water is not added in reaction at last.
Table 2 carries out for the synthetic polyquaternium cation compound of various embodiments of the present invention the analytical results that viscosity and nitrogen content etc. detect, wherein solid content is to adopt the acetone Determination by Stripping, wherein product viscosity is with deionized water, the solid content of product to be diluted to 10% rear mensuration, and the benchmark of nitrogen content numerical value is the product solid substance.
Table 2
Table 3 be adopt the shampoo formula that the synthetic polyquaternium of the embodiment of the present invention prepares and adopt that contrast product (the PQ-10 product that existing market is used) prepares the detected result contrast table of the performances such as viscosity, foam, transparency of shampoo formula, wherein formulation Example 1 adopts the product of embodiment 1 as the preparation of raw material shampoo, formulation Example 2 adopts the product of embodiment 2, the like, comparative example be adopt contrast use be purchased product as raw material.
Table 3
Table 4 is the hair washing effect assessment contrast table (volunteer is 10 people, 1 male 9 female) of the shampoo formula of the synthetic polyquaternium of the embodiment of the present invention 5 and contrast product (the PQ-10 product that existing market is used).
Show by above comparative test result, novel polyquaternium of the present invention has good flexibility, conditioning property, moisture-keeping functions and is easy to the rinsing function hair.
Claims (9)
1. one kind contains replacing or random copolymers of quaternary ammonium salt side group, this polymkeric substance is that random or alternating copolymer take alpha-olefin and unsaturated dicarboxylic anhydride is as skeleton, generate through trimethylamine generation imidization and/or esterification with the trimethylamine that contains primary amine groups and/or hydroxyl the derivative that contains tertiary amine group, last and alkylating reagent carries out quaterisation and obtains, and this multipolymer comprises: 1) the structural unit A of 45～60mol%; 2) structural unit B and/or the E of 20～55mol%; 3) the structural unit C of 〉=0mol%～10mol%; 4) the structural unit D of 〉=0mol%～10mol%, these percentage ratios are based on the total mole number of the entire infrastructure unit in copolymer skeleton:
Wherein:
R and R
5Be straight or branched C independently of one another
2-C
10Alkylidene group;
R
1, R
2And R
3Can be identical or different, be C independently of one another
1-C
6Alkyl, C
2-C
6Thiazolinyl or C
6-C
8Aralkyl, these groups are unsubstituted or are replaced by hydroxyl or amino;
R
4Be C
4～C
20Alkyl or C
6～C
20Aralkyl;
M is unsaturated dicarboxylic anhydride residue;
A
-Be one or more in halide anion, sulfate group or carbonate group;
Carboxyl in D, E and F structural unit can be not neutralize, and can be also part neutralization or all neutralizations.
2. multipolymer claimed in claim 1, its number-average molecular weight is 2550～350000.
Claimed in claim 1 contain the quaternary ammonium salt side group alternately or the preparation method of random copolymers, the method comprises: based on the total mole number of alpha-olefin and unsaturated dicarboxylic anhydride, allow the unsaturated dicarboxylic anhydride of the alpha-olefin of 45～60mol% and 40～55mol% carry out alternating polymerization or random copolymerization to prepare random or alternating copolymer, then allow this multipolymer and the trimethylamine H that contains primary amine groups
2N-R-NR
1R
2And/or the trimethylamine HO-R of hydroxyl
5-NR
1R
2Imidization and/or esterification occur generate the multipolymer that contains pendant tertiary amine group group, last and alkylating reagent R
3A carry out quaterisation and obtain containing the quaternary ammonium salt side group alternately or random copolymers,
Wherein R and R
5Be straight or branched C independently of one another
2-C
10Alkylidene group; With
R
1, R
2And R
3Can be identical or different, be C independently of one another
1-C
6Alkyl, C
2-C
6Thiazolinyl or C
6-C
8Aralkyl, these groups are unsubstituted or are replaced by hydroxyl or amino.
4. according to claim 3 method, wherein the alkylating reagent R that uses of quaterisation
3A is the R that meets the following conditions
3A: wherein A is halogen Cl, Br or I, and R
3C
1-C
6Alkyl, C
2-C
6Thiazolinyl or C
6-C
8Aralkyl; Or A is sulfate group R
3OSO
3-or carbonate group R
3OCO
2-, i.e. R
3A is sulfuric ester R
3OSO
3-R
3Or carbonic ether R
3OCO
2-R
3, two R wherein
3C independently of one another
1-C
6Alkyl, C
2-C
6Thiazolinyl or C
6-C
8Aralkyl.
5. according to claim 3 method, is characterized in that alpha-olefin is CH
2=CHR
4, R wherein
4Be C
4～C
20Alkyl or C
6～C
20Aralkyl.
6. according to claim 3 method, wherein unsaturated dicarboxylic anhydride is one or more in maleic anhydride, methyl-maleic acid acid anhydride, laurylene Succinic anhydried and Tetra Hydro Phthalic Anhydride.
7. any one described preparation method according to claim 3-6, it comprises the following steps:
A) alpha-olefin and unsaturated dicarboxylic anhydride are joined in reactor, temperature of reaction is controlled at 130～220 ℃, reacts after 7～24 hours, is replaced or random copolymers;
B) with steps A) multipolymer that obtains of polymerization joins in polyethers as reaction solvent, stir, add the trimethylamine that contains primary amine group, control 60～200 ℃ of temperature of reaction, reacted 2～9 hours, and remove the water that dereaction produces, make part or all of maleic anhydride unit generation imidization reaction; Or
With steps A) multipolymer that obtains of polymerization joins in polyethers as reaction solvent, stir, add the trimethylamine that contains hydroxyl, control 60～200 ℃ of temperature of reaction, reacted 2～9 hours, and made part or all of maleic anhydride unit generation single-esterification;
C) at step B) add alkylating reagent in the multipolymer that contains tertiary amine group that obtains of reaction, make part or all of tertiary amine group carry out quaterisation, control 70～150 ℃ of temperature of reaction, randomly, add a certain amount of deionized water to be adjusted to required solid content after reaction, randomly, carry out the adjusting of pH value with alkaline matter.
Power and require 1 described contain the quaternary ammonium salt side group alternately or random copolymers in personal-care supplies, makeup or cleaning product as the purposes of amendment, softening agent and membrane-forming agent.
Claimed in claim 1 contain the quaternary ammonium salt side group alternately or the application of random copolymers in papermaking, water treatment, printing and dyeing and fabric treating field.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 201010597385 CN102153690B (en) | 2010-12-20 | 2010-12-20 | Alternating or random copolymer containing polyquaternium lateral group and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 201010597385 CN102153690B (en) | 2010-12-20 | 2010-12-20 | Alternating or random copolymer containing polyquaternium lateral group and preparation method thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN102153690A CN102153690A (en) | 2011-08-17 |
| CN102153690B true CN102153690B (en) | 2013-06-12 |
Family
ID=44435393
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN 201010597385 Active CN102153690B (en) | 2010-12-20 | 2010-12-20 | Alternating or random copolymer containing polyquaternium lateral group and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN102153690B (en) |
Families Citing this family (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108997521A (en) * | 2018-06-20 | 2018-12-14 | 深圳市广昌达石油添加剂有限公司 | A kind of multiple copolymer and preparation method thereof as pour point depression of crude oil thinner |
| CN111690143B (en) * | 2020-06-23 | 2022-08-05 | 新乡市瑞丰新材料股份有限公司 | Preparation method of high molecular weight high-nitrogen ashless dispersant |
| CN111944198A (en) * | 2020-07-24 | 2020-11-17 | 江苏海云花新材料有限公司 | Cationic quaternary ammonium salt antistatic agent |
| CN112603855A (en) * | 2020-12-18 | 2021-04-06 | 江南大学 | Method for preparing hair product for replacing silicone oil |
| CN113083032B (en) * | 2021-04-26 | 2022-10-28 | 贵州省材料产业技术研究院 | Positively charged blended ultrafiltration membrane and preparation method thereof |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE10104470A1 (en) * | 2001-02-01 | 2002-08-08 | Basf Ag | Detergent formulations to prevent discoloration of plastic objects |
| EP1449893A1 (en) * | 2003-02-21 | 2004-08-25 | Fuji Photo Film Co., Ltd. | Electrostatic inkjet ink composition |
| WO2006079628A2 (en) * | 2005-01-28 | 2006-08-03 | Basf Aktiengesellschaft | Method for applying integrated pre-treatment layers containing dicarboxylic acid olefin copolymers to metallic surfaces |
| WO2010014655A1 (en) * | 2008-07-31 | 2010-02-04 | The Lubrizol Corporation | Novel copolymers and lubricating compositions thereof |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH09124868A (en) * | 1995-10-31 | 1997-05-13 | Nippon Oil & Fats Co Ltd | Chlorine-containing resin composition |
-
2010
- 2010-12-20 CN CN 201010597385 patent/CN102153690B/en active Active
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE10104470A1 (en) * | 2001-02-01 | 2002-08-08 | Basf Ag | Detergent formulations to prevent discoloration of plastic objects |
| EP1449893A1 (en) * | 2003-02-21 | 2004-08-25 | Fuji Photo Film Co., Ltd. | Electrostatic inkjet ink composition |
| WO2006079628A2 (en) * | 2005-01-28 | 2006-08-03 | Basf Aktiengesellschaft | Method for applying integrated pre-treatment layers containing dicarboxylic acid olefin copolymers to metallic surfaces |
| WO2010014655A1 (en) * | 2008-07-31 | 2010-02-04 | The Lubrizol Corporation | Novel copolymers and lubricating compositions thereof |
Non-Patent Citations (1)
| Title |
|---|
| Martinez Francisco et al.Copolymerization of maleic anhydride with styrene and α-olefins.Molecular and thermal characterization.《Journal of Macromolecular Science, Part A: Pure and Applied Chemistry》.2005,第A42卷(第8期),全文. * |
Also Published As
| Publication number | Publication date |
|---|---|
| CN102153690A (en) | 2011-08-17 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN102153690B (en) | Alternating or random copolymer containing polyquaternium lateral group and preparation method thereof | |
| US9090727B2 (en) | Rheology modifier polymer | |
| EP2933280B1 (en) | Rheology modifier polymer | |
| JP4689774B2 (en) | Amphoteric electrolyte polymer for body care products | |
| CN101959494B (en) | Hair washing composition | |
| CN105518038A (en) | Solid polymer composition obtained by polymerization of an acid group-containing monomer in the presence of a polyether compound | |
| CN103797102A (en) | Detergent compositions comprising sustainable surfactant systems comprising isoprenoid-derived surfactants | |
| US8003088B2 (en) | Copolymer and detergent composition employing it | |
| MX2014005089A (en) | Graft dendrite copolymers, and methods for producing the same. | |
| KR20080077983A (en) | Water-soluble copolymer having alkyl-modified carboxyl group | |
| ES2232901T5 (en) | High molecular weight cationic copolymers | |
| US20190040172A1 (en) | Aqueous emulsion polymers as rheology modifiers, compositions thereof, and method of use | |
| CN102766236A (en) | Linear precipitated polymer | |
| CN105143290A (en) | Alkaline-swellable emulsion polymers | |
| US20080033129A1 (en) | Polymeric viscosity modifiers | |
| CN105154245B (en) | A kind of liquid detergent of stripping header composition and its manufacture method and application the stripping header composition | |
| CN102002445A (en) | Washing powder and soap powder viscosity reduction synergist | |
| CN105189589A (en) | Polymers prepared from alkoxylated polyamines | |
| JPWO2020085134A1 (en) | Topical composition | |
| CN103269682A (en) | Cationic polymer latexes and uses | |
| JP4316426B2 (en) | Cleaning composition | |
| JP2009275010A (en) | Skin cleanser composition | |
| US20220192966A1 (en) | A personal washing composition and method of achieving improved conditioning benefits | |
| Girase et al. | Process Development Studies for Synthesis of Poly (Dadmac) Cationic Homopolymer and its Characterizations as Hair Care Surfactant | |
| JP2006169355A (en) | Cleanser composition |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant |