MXPA99008947A - Polymers with thiol terminal function - Google Patents
Polymers with thiol terminal functionInfo
- Publication number
- MXPA99008947A MXPA99008947A MXPA/A/1999/008947A MX9908947A MXPA99008947A MX PA99008947 A MXPA99008947 A MX PA99008947A MX 9908947 A MX9908947 A MX 9908947A MX PA99008947 A MXPA99008947 A MX PA99008947A
- Authority
- MX
- Mexico
- Prior art keywords
- polymer
- group
- carbon atoms
- chr
- branched
- Prior art date
Links
- 229920000642 polymer Polymers 0.000 title claims abstract description 96
- 125000003396 thiol group Chemical class [H]S* 0.000 title 1
- 239000000412 dendrimer Substances 0.000 claims abstract description 64
- 229920000736 dendritic polymer Polymers 0.000 claims abstract description 64
- 229920000587 hyperbranched polymer Polymers 0.000 claims abstract description 42
- 125000000524 functional group Chemical group 0.000 claims abstract description 13
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 claims abstract description 10
- 239000003963 antioxidant agent Substances 0.000 claims abstract description 9
- 125000004122 cyclic group Chemical group 0.000 claims abstract description 8
- 125000004430 oxygen atoms Chemical group O* 0.000 claims abstract description 8
- 150000002148 esters Chemical class 0.000 claims abstract description 5
- 229910052757 nitrogen Inorganic materials 0.000 claims abstract description 4
- 125000004442 acylamino group Chemical group 0.000 claims abstract description 3
- 125000005842 heteroatoms Chemical group 0.000 claims abstract description 3
- 229910052760 oxygen Inorganic materials 0.000 claims abstract description 3
- 150000003839 salts Chemical class 0.000 claims abstract description 3
- 239000011780 sodium chloride Substances 0.000 claims abstract description 3
- 229920002873 Polyethylenimine Polymers 0.000 claims description 40
- 238000006243 chemical reaction Methods 0.000 claims description 30
- 125000004432 carbon atoms Chemical group C* 0.000 claims description 28
- 239000000203 mixture Substances 0.000 claims description 18
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 18
- 238000000034 method Methods 0.000 claims description 15
- 125000004435 hydrogen atoms Chemical group [H]* 0.000 claims description 13
- FAYOCELKCDKZCA-UHFFFAOYSA-N 5-hydroxy-2,4-dimethylthiophen-3-one Chemical compound CC1SC(O)=C(C)C1=O FAYOCELKCDKZCA-UHFFFAOYSA-N 0.000 claims description 9
- 230000000875 corresponding Effects 0.000 claims description 9
- 230000000269 nucleophilic Effects 0.000 claims description 8
- CNHYKKNIIGEXAY-UHFFFAOYSA-N thiolan-2-imine Chemical compound N=C1CCCS1 CNHYKKNIIGEXAY-UHFFFAOYSA-N 0.000 claims description 7
- 229920001281 polyalkylene Polymers 0.000 claims description 6
- 239000002253 acid Substances 0.000 claims description 5
- 150000001875 compounds Chemical class 0.000 claims description 5
- 229920000768 polyamine Polymers 0.000 claims description 5
- MDFFNEOEWAXZRQ-UHFFFAOYSA-N Amino radical Chemical compound [NH2] MDFFNEOEWAXZRQ-UHFFFAOYSA-N 0.000 claims description 4
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 4
- 238000004519 manufacturing process Methods 0.000 claims description 4
- 229920000728 polyester Polymers 0.000 claims description 4
- 238000006467 substitution reaction Methods 0.000 claims description 4
- PMNLUUOXGOOLSP-UHFFFAOYSA-N 2-mercaptopropanoic acid Chemical compound CC(S)C(O)=O PMNLUUOXGOOLSP-UHFFFAOYSA-N 0.000 claims description 3
- XUJNEKJLAYXESH-REOHCLBHSA-N L-cysteine Chemical compound SC[C@H](N)C(O)=O XUJNEKJLAYXESH-REOHCLBHSA-N 0.000 claims description 3
- CWERGRDVMFNCDR-UHFFFAOYSA-N Thioglycolic acid Chemical compound OC(=O)CS CWERGRDVMFNCDR-UHFFFAOYSA-N 0.000 claims description 3
- 125000004103 aminoalkyl group Chemical group 0.000 claims description 3
- 229910052799 carbon Inorganic materials 0.000 claims description 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 3
- 239000002537 cosmetic Substances 0.000 claims description 3
- 235000018417 cysteine Nutrition 0.000 claims description 3
- 239000003638 reducing agent Substances 0.000 claims description 3
- 125000004417 unsaturated alkyl group Chemical group 0.000 claims description 3
- 239000004952 Polyamide Substances 0.000 claims description 2
- 125000000217 alkyl group Chemical group 0.000 claims description 2
- 239000003849 aromatic solvent Substances 0.000 claims description 2
- 125000004429 atoms Chemical group 0.000 claims description 2
- 150000007522 mineralic acids Chemical class 0.000 claims description 2
- 150000007524 organic acids Chemical class 0.000 claims description 2
- 229920002647 polyamide Polymers 0.000 claims description 2
- 239000011528 polyamide (building material) Substances 0.000 claims description 2
- RAOIDOHSFRTOEL-UHFFFAOYSA-N Tetrahydrothiophene Chemical compound C1CCSC1 RAOIDOHSFRTOEL-UHFFFAOYSA-N 0.000 claims 1
- 230000003078 antioxidant Effects 0.000 claims 1
- 150000001735 carboxylic acids Chemical class 0.000 claims 1
- CNHYKKNIIGEXAY-UHFFFAOYSA-O thiolan-2-ylideneazanium Chemical compound [NH2+]=C1CCCS1 CNHYKKNIIGEXAY-UHFFFAOYSA-O 0.000 claims 1
- 230000000111 anti-oxidant Effects 0.000 abstract description 8
- 150000001732 carboxylic acid derivatives Chemical class 0.000 abstract description 2
- 150000001335 aliphatic alkanes Chemical group 0.000 abstract 3
- 125000000008 (C1-C10) alkyl group Chemical group 0.000 abstract 1
- 229910052500 inorganic mineral Inorganic materials 0.000 abstract 1
- 239000011707 mineral Substances 0.000 abstract 1
- 239000012038 nucleophile Substances 0.000 abstract 1
- 239000007864 aqueous solution Substances 0.000 description 42
- 239000008346 aqueous phase Substances 0.000 description 34
- 239000000047 product Substances 0.000 description 26
- 239000011149 active material Substances 0.000 description 20
- 150000003141 primary amines Chemical group 0.000 description 19
- 150000003573 thiols Chemical group 0.000 description 17
- 238000003756 stirring Methods 0.000 description 15
- 239000000178 monomer Substances 0.000 description 12
- PIICEJLVQHRZGT-UHFFFAOYSA-N 1,2-ethanediamine Chemical compound NCCN PIICEJLVQHRZGT-UHFFFAOYSA-N 0.000 description 10
- UGYLGQZOILUENF-UHFFFAOYSA-N C1(CC(C)O1)=S Chemical compound C1(CC(C)O1)=S UGYLGQZOILUENF-UHFFFAOYSA-N 0.000 description 10
- KEAYESYHFKHZAL-UHFFFAOYSA-N sodium Chemical compound [Na] KEAYESYHFKHZAL-UHFFFAOYSA-N 0.000 description 10
- 229910052708 sodium Inorganic materials 0.000 description 10
- 239000011734 sodium Substances 0.000 description 10
- 229920000962 poly(amidoamine) Polymers 0.000 description 6
- 210000004209 Hair Anatomy 0.000 description 5
- NRFJZTXWLKPZAV-UHFFFAOYSA-N N-(2-oxothiolan-3-yl)acetamide Chemical compound CC(=O)NC1CCSC1=O NRFJZTXWLKPZAV-UHFFFAOYSA-N 0.000 description 5
- 210000004940 Nucleus Anatomy 0.000 description 5
- 229960004753 citiolone Drugs 0.000 description 5
- 238000004809 thin layer chromatography Methods 0.000 description 5
- 241000284156 Clerodendrum quadriloculare Species 0.000 description 4
- 210000003491 Skin Anatomy 0.000 description 4
- 238000007792 addition Methods 0.000 description 4
- 125000003277 amino group Chemical group 0.000 description 4
- RTZKZFJDLAIYFH-UHFFFAOYSA-N diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 4
- 239000006210 lotion Substances 0.000 description 4
- CERQOIWHTDAKMF-UHFFFAOYSA-M methacrylate Chemical compound CC(=C)C([O-])=O CERQOIWHTDAKMF-UHFFFAOYSA-M 0.000 description 4
- OKKJLVBELUTLKV-UHFFFAOYSA-N methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 4
- 238000002360 preparation method Methods 0.000 description 4
- 230000015572 biosynthetic process Effects 0.000 description 3
- 239000006071 cream Substances 0.000 description 3
- 239000000499 gel Substances 0.000 description 3
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 3
- QTKAQJWFVXPIFV-YFKPBYRVSA-N methyl (2R)-2-acetamido-3-sulfanylpropanoate Chemical compound COC(=O)[C@H](CS)NC(C)=O QTKAQJWFVXPIFV-YFKPBYRVSA-N 0.000 description 3
- 150000004702 methyl esters Chemical class 0.000 description 3
- -1 methylene, ethylene, propylene, methylpropylene, ethylpropylene, tetramethylene, pentamethylene, hexamethylene, phenylene Chemical group 0.000 description 3
- 230000003647 oxidation Effects 0.000 description 3
- 238000007254 oxidation reaction Methods 0.000 description 3
- 239000000843 powder Substances 0.000 description 3
- 230000002829 reduced Effects 0.000 description 3
- BMLMGCPTLHPWPY-REOHCLBHSA-N (4R)-2-oxo-1,3-thiazolidine-4-carboxylic acid Chemical compound OC(=O)[C@@H]1CSC(=O)N1 BMLMGCPTLHPWPY-REOHCLBHSA-N 0.000 description 2
- 210000000282 Nails Anatomy 0.000 description 2
- 150000001412 amines Chemical class 0.000 description 2
- 239000003153 chemical reaction reagent Substances 0.000 description 2
- 150000002019 disulfides Chemical class 0.000 description 2
- 238000005755 formation reaction Methods 0.000 description 2
- LRHPLDYGYMQRHN-UHFFFAOYSA-N n-butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- 239000012071 phase Substances 0.000 description 2
- 238000006116 polymerization reaction Methods 0.000 description 2
- 239000000243 solution Substances 0.000 description 2
- 241000894007 species Species 0.000 description 2
- YXFVVABEGXRONW-UHFFFAOYSA-N toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 2
- ZOBPZXTWZATXDG-UHFFFAOYSA-N 1,3-thiazolidine-2,4-dione Chemical compound O=C1CSC(=O)N1 ZOBPZXTWZATXDG-UHFFFAOYSA-N 0.000 description 1
- REYLLNRLWCBKCM-UHFFFAOYSA-N 2-acetamido-4-sulfanylbutanoic acid Chemical compound CC(=O)NC(C(O)=O)CCS REYLLNRLWCBKCM-UHFFFAOYSA-N 0.000 description 1
- BMLMGCPTLHPWPY-UHFFFAOYSA-N 2-oxo-1,3-thiazolidine-4-carboxylic acid Chemical compound OC(=O)C1CSC(=O)N1 BMLMGCPTLHPWPY-UHFFFAOYSA-N 0.000 description 1
- 229960004308 ACETYLCYSTEINE Drugs 0.000 description 1
- 210000002615 Epidermis Anatomy 0.000 description 1
- 210000004709 Eyebrows Anatomy 0.000 description 1
- 102000011782 Keratins Human genes 0.000 description 1
- 108010076876 Keratins Proteins 0.000 description 1
- PWKSKIMOESPYIA-BYPYZUCNSA-N L-N-acetyl-Cysteine Chemical compound CC(=O)N[C@@H](CS)C(O)=O PWKSKIMOESPYIA-BYPYZUCNSA-N 0.000 description 1
- 239000004472 Lysine Substances 0.000 description 1
- 210000004080 Milk Anatomy 0.000 description 1
- 108010039918 Polylysine Proteins 0.000 description 1
- 239000003377 acid catalyst Substances 0.000 description 1
- 125000003158 alcohol group Chemical group 0.000 description 1
- 238000007112 amidation reaction Methods 0.000 description 1
- 229920001400 block copolymer Polymers 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 238000009833 condensation Methods 0.000 description 1
- 230000005494 condensation Effects 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 230000001809 detectable Effects 0.000 description 1
- 238000002845 discoloration Methods 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 238000001962 electrophoresis Methods 0.000 description 1
- 239000000839 emulsion Substances 0.000 description 1
- 239000002360 explosive Substances 0.000 description 1
- 239000012467 final product Substances 0.000 description 1
- 238000009472 formulation Methods 0.000 description 1
- 239000008266 hair spray Substances 0.000 description 1
- 230000000977 initiatory Effects 0.000 description 1
- KFZMGEQAYNKOFK-UHFFFAOYSA-N iso-propanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 1
- 230000004301 light adaptation Effects 0.000 description 1
- 125000003588 lysine group Chemical group [H]N([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])(N([H])[H])C(*)=O 0.000 description 1
- 235000013336 milk Nutrition 0.000 description 1
- 239000008188 pellet Substances 0.000 description 1
- 239000008194 pharmaceutical composition Substances 0.000 description 1
- 229920000333 poly(propyleneimine) Polymers 0.000 description 1
- 238000006068 polycondensation reaction Methods 0.000 description 1
- 229920000656 polylysine Polymers 0.000 description 1
- 230000002335 preservative Effects 0.000 description 1
- 239000003755 preservative agent Substances 0.000 description 1
- 230000001681 protective Effects 0.000 description 1
- 239000012429 reaction media Substances 0.000 description 1
- 239000011541 reaction mixture Substances 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 125000000467 secondary amino group Chemical class [H]N([*:1])[*:2] 0.000 description 1
- 239000002453 shampoo Substances 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 230000002194 synthesizing Effects 0.000 description 1
- 238000010189 synthetic method Methods 0.000 description 1
- 230000001988 toxicity Effects 0.000 description 1
- 231100000419 toxicity Toxicity 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
- HCHKCACWOHOZIP-UHFFFAOYSA-N zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 1
Abstract
The invention concerns novel polymers selected among hyperbranched polymers and dendrimers comprising functional groups of formula (I) in which:Y represents the oxygen atom or a NH group;A represents a linear, branched or cyclic C1-C12 di-yl alkane group, saturated or unsaturated;this di-yl alkane group can optionally be interrupted by one or several heteroatoms, such as O or N;this di-yl alkane group can optionally be substituted by a function:amino:-NH2, optionally in the form of a mineral or organic salt, acylamino:-NH-COR, in which R represents a linear, branched or cyclic C1-C10 alkyl group, saturated or unsaturated, carboxylic acid, C1-C10 ester;X represents a nucleophile group. The invention also concerns a method for preparing them and the use of said dendrimers and/or hyperbranched polymers as antioxidants.
Description
POLYMERS WITH AN ERMINAL TIOL FUNCTION
DESCRIPTION OF THE INVENTION
The invention relates to novel hyperbranched dendrimers and polymers containing thiol functional groups, to a process for their preparation and to the use of these dendrimers and / or hyperbranched polymers as antioxidants. Many hyperbranched polymers and dendrimers have already been described. Reference may be made, for example to: D.A. Tomalia et al., Angew. Chem. Int. Engl. 2_9 (1990) 138-175; N. Ardoin and D. Astruc, Bull. Soc. Chim. F. (1995) 132, 875-909; BI. Voit, Acta Polymer, 4_6, 87-99 (1995). The possibility of preparing dendrimers containing thiol end groups has been covered by certain authors, such as, for example, D.A. Tomalia in US-4,587,329 and EP-A-234, 408, although this preparation has never been done effectively, nor does it have the surprising properties, demonstrated by the Applicant, of these molecules mentioned or suggested in the prior art. In addition, the process for preparing hyperbranched polymers and dendrimers containing groups
REF .: 31307 functional is novel and has many advantages, among which are the good synthetic performance, the use of commercially available starting materials and the ease of implementation. Hyperbranched polymers are molecular constructs that have a branched structure, generally around a nucleus. Their structure is generally devoid of symmetry: the monomer or base units involved in the construction of the hyperbranched polymer may be varied in nature and distributed non-uniformly. The branches in the polymer can be of varied nature and length. The number of base units, or monomers, may be different according to the different branch. As long as they remain asymmetric, the hyperbranched polymers can have: an extremely branched structure, around a core; successive generations or branching layers; a layer of end chains. Hyperbranched polymers are generally obtained from the polycondensation of one or more monomers ABx, A and B which are reactive groups capable of reacting with each other, x is an integer greater than or equal to 2, but other processes can be devised preparation. The hyperbranched polymers are characterized by their degree of polymerization DP = 1-b, b which is the percentage of the nonterminal functional groups in B that have not reacted with a group A. Since the condensation is not systematic, in contrast to the Dendrimer synthesis, the degree of polymerization is less than 100%. Usually, by the known synthetic methods, DP is between 15 and 90%. An end-T group can react with the hyperbranched polymer to obtain a specific functionality at the end of the chains. Such polymers are described in particular in B.I. Voit, Acta Polymer, _6, 87-99 (1995); EP-682,059, O-96/14346; O-96/14345; WO96 / 12754. Several hyperbranched polymers can be combined with each other, via a covalent bond or other type of link, via their end groups. Such so-called "bridged" polymers are within the definition of the hyperbranched polymers according to the present invention. The dendrimers are highly branched polymers and oligomers that are also known; they have a well-defined chemical structure and are said to be "perfect" hyperbranched polymers. As a general rule, the dendrimers comprise a core, a certain number of generations of branches, or axes, and terminal groups. The general axes consist of structural units that are identical for the same generation of axes and can be identical or different for different generations of axes. Generations of axes extend radially in a geometric progression of the nucleus. The terminal groups of a dendrimer of the generation Nh are the terminal functional groups of the axes of the generation Nth or terminal generation. Such polymers are described in particular in D.A. Tomalia, A.M. Naylor and W.A. Goddard III, Angewandt e Chemi e, Int. Ed. Engl. 29_, 138-175 (1990); C.J. "Hawker and J.M.J.
Frechet, J. Am. Chem. Soc, 112, 7638 (1990); BI.
Voit, Acta polymer, 4_6, 87-99 (1995); N. Ardoin and
D. Astruc. Bull. Soc. Chim. Fr. 132, 875-909 (1995). The dendrimers can also, more particularly, be defined by the following formula (DI):
C [AÍBÍ (A2B2 (... (Aa-iBn-x (^ (T) rn) r ^) r "_2 ...) r2) rx] s (DI) in which:
C represents the core, linked by a number s of functional groups to axes A1B1 via groups Ai; s is an integer greater than or equal to 1 and less than or equal to the number of. functional groups in C; for each axis (AiBi) (i = 1, 2 ... n), the group Bi is linked to r groups Ai + 1 of an axis (Ai +? Bi +?); each group R (i> 2) is linked to a simple group Bi-! of the axis (Í_IBÍ_I); - r ± (i = 1, 2 .... n-l) represents the number of functional groups in group B ± belonging to the axis (iBi), ri which is an integer greater than or equal to 2; - the index i (i = 1, 2 .... n) is an integer which denotes the generation of each axis; the generation axis nth AnBn is chemically linked to a number rn of the terminal groups T, rn which is an integer greater than or equal to zero. The definition of dendrimer given in the above includes molecules that contain symmetric branching; it also includes molecules containing non-symmetric branching such as, for example, dendrimers whose axes are lysine groups, in which the branching of a generation of axes on the preceding generation is carried out on the amin amines of the lysine, which leads to a difference in the length of the axes for the different branch. Dense star polymers, explosive star polymers and rod-shaped dendrimers are included in the present definition of dendrimers. The molecules known as arboroles and cascading molecules are also within the definition of the dendrimers according to the present invention. Various dendrimers can be combined together, via a covalent bond or other type of bond, via their terminal groups to give species known as "bridged dendrimers" or "dendrimer aggregates". Such species are included in the definition of dendrimers according to the present invention. The dendrimers may be in the form of a group of molecules of the same generation, these are so-called monodispersed mono groups; they can also be in the form of groups of different generations, which are known as polydispersed groups. The definition of dendrimers according to the present invention includes monodispersed groups as well as polydispersed dendrimer groups. The object of the invention is novel polymers selected from hyperbranched polymers and dendrimers, characterized in that they contain functional groups corresponding to formula (I):
Y
II
HS-A-C- (I)
wherein: * Y represents an oxygen atom or an NH group, preferably Y = 0, * A represents a linear, branched or cyclic, saturated or unsaturated alkanedi group of 1 to 12 carbon atoms; this alkandiyl group can be optionally interrupted by one or more heteroatoms, such as
O or N; this alkandiyl group can be optionally substituted with one of the following amino functions: -NH2, optionally in the form of a salt of an inorganic or organic acid, acylamino: -NH-COR, in which R represents a linear, branched alkyl group or cyclic, saturated or unsaturated of 1 to 10 carbon atoms, carboxylic acid, - ester of 1 to 10 carbon atoms; * X represents a nucleophilic group, preferably either an oxygen atom or a group -NR '- in which R' is selected from a hydrogen atom; a linear or branched, saturated or unsaturated alkyl group of 1 to 6 carbon atoms; a linear or branched, saturated or unsaturated mono- or polyhydroxyalkyl group of 1 to 6 carbon atoms; an aminoalkyl group of 1 to 6 carbon atoms or a polyalkyleneimine group. For example, A can be a methylene, ethylene, propylene, methylpropylene, ethylpropylene, tetramethylene, pentamethylene, hexamethylene, phenylene, phenyldiyl group, etc. Advantageously, A represents a radical corresponding to one of formulas (a) to (d) below:
-CHR1-CHR2-CHR3- (a)
-CHR '1-CHR'2-CHR'r 3-CHR'4- (b) - (CHR' '') k- (CHR '', 2) -CH (C02H) -NH- (d) in which * R1, R2, R3, R'1, R'2, R'3, R'4, R '' 'and R' '' 2, which may be identical or different, represent: a hydrogen atom, a linear, branched or cyclic, saturated or unsaturated alkyl radical of 1 to 6 carbon atoms, an amino radical -NH2, a carboxylic acid radical -COOH, an alkylamino radical of 1 to 10 carbon atoms, an acylamino radical of 1 to 10 carbon atoms; * R''1, R''2, R''3 and R''4, which may be identical or different, represent: a hydrogen atom, a linear or branched, saturated or unsaturated alkyl radical of 1 to 4 atoms of carbon, the arrows indicating the positions of the substitutions in the formula (c), k is an integer, preferably k = 0 or 1. Preferably, A is chosen from: -CH2-CH (C02H) -NH - and Y = 0 - (CH2) 2- (CH3CONH) CH- and Y = 0 - (CH2) 3- and Y = 0 or Y = NH Advantageously, A is the trimethylene radical -CH2-CH2-CH2-, and Y = 0, the compound according to the invention corresponding in this case to the following formula (II):
wherein: X represents a nucleophilic group, preferably either an oxygen atom or a group -NR '- in which R' a hydrogen atom is chosen; a linear or branched, saturated or unsaturated alkyl group of 1 to 6 carbon atoms; a mono- or polyhydroxyalkyl group, linear or branched, saturated or unsaturated; an aminoalkyl group of 1 to 6 carbon atoms or a polyalkylene group. Preferably, according to the invention, X is chosen from an oxygen atom and an NH group. In the case of the dendrimers, the nucleophilic group X is generally an end functional group. In the case of hyperbranched polymers such as, for example, polyethyleneimine, the X group can be a secondary amine found in one of the polymer branches without being in the end position.
Advantageously, according to the invention, at least 10% are grafted, in numerical terms, of the X groups of the hyperbranched polymer or of the dendrimer with a functional group:
O II HS-C H-C H-C Hj-C
and even more preferably at least 40%. The percentage of thiol functional groups relative to the total number of functional groups X in the hyperbranched polymer or dendrimer which are capable of being replaced by a group:
OR 11 HS-CH-CH-CHj-C
it is adapted as a function of the other characteristics of the hyperbranched polymer or dendrimer, in particular the number of generations and the nature of the axes, and as a function of the expected properties, in particular the solubility of the hyperbranched polymer or dendrimer. Such adaptations are within the scope of a person skilled in the art by simple tests.
The object of the invention is also a first process for preparing hyperbranched polymers and dendrimers containing thiol end groups, this process is characterized in that a starting polymer chosen from hyperbranched polymers and dendrimers is reacted in which the groups or chains of end contain a nucleophilic function, with a thiolactone or an iminothiolane according to the following reaction scheme:
0- (XH) n + mx H) m in which
@ - (XH) n
represents a dendrimer or a hyperbranched polymer containing n HX functions, as defined above, m is an integer m < ^ n and A represents a radical corresponding to one of the formulas (a) to (d) below:
-CHR1-CHR2-CHR3- (a) -CHR ^ -CHR ^ -CHR '3-CHR'4- (b) - (CHR' "'J (CHR' '') -CH (C02H) -NH- (d)
in which R1, R 'R R' R 'R' R 'R'
R '' '2, which may be identical or different, represent: a hydrogen atom, a linear or branched alkyl radical, saturated or unsaturated of 1 to 6 carbon atoms, an amino radical -NH2, a radical carboxylic acid -COOH , an alkylamino radical of 1 to 10 carbon atoms; R r r 1 R r t 2
R "'3 and R" 4, which may be identical or different, represent: a hydrogen atom, a linear or branched, saturated or unsaturated alkyl radical of 1 to 4 carbon atoms, the arrows indicating the positions of the substitutions in the formula (c), k is an integer, preferably k = 0 or 1. Preferably, in the process according to the invention, the compound
is chosen from 2-oxo-4-thiazolidinecarboxylic acid, also known as procysteine:
N-acetylhomocysteintiolactone
? -thiobutyrolactone:
iminothiolane
Advantageously, in the process according to the invention, a reagent chosen from procysteine, N-acetylhomocysteintiolactone and? -thiobutyrolactone is used.
Advantageously, in the process according to the invention, the compound is? -thiobutyrolactone, which is a commercial product. The reaction for opening the thiolactone or iminothiolane is generally carried out under an inert atmosphere either in water or in an aromatic solvent such as toluene or an alcohol such as methanol, ethanol, isopropanol or butanol, and, depending on the boiling point of the solvent, at a temperature between 0 ° C and 110 ° C. However, according to a preferred form of the invention, a reaction is carried out in water and, in this case, the dendrimer or the hyperbranched polymer and the thiolactone or the iminothiolane are mixed in stoichiometric proportions (in relation to the -XH functions of the polymer) and then the mixture is brought, under an inert atmosphere, to a temperature between 0 ° C and 110 ° C. When the free amino or hydroxyl functions are allowed to remain between the n functional groups of the hyperbranched polymer or dendrimer, the desired amount m of thiolactone or iminothiolane molecules per molecule of the dendrimer or hyperbranched polymer molecule is used in order to obtain the dendrimer or hyperbranched polymer that has nm free amino or hydroxyl functions and m thiol functions. Depending on the basicity of the dendrimer or the hyperbranched polymer, the reaction time can be between 1 and 48 hours, the progress of the reaction is monitored by testing the appearance of the thiol and / or the disappearance of the amine or alcohol function function. It is also possible to monitor the conversion of the starting polymer by electrophoresis. Advantageously, when the radical -A- contains a free acid function or a free amine function, this function is neutralized before introducing the starting polymer into the reaction medium. If, during the reaction, a certain amount of thiol is oxidized to the corresponding disulfide, the reaction mixture is then diluted with twice its volume of water and stirred in acid medium in the presence of zinc powder for 1 to 3 hours. With most of the disulfide that has been reduced, the mixture is then filtered and a solution of the expected compound which can be used directly is obtained. Dendrimers and hyperbranched polymers containing a mercaptoalkylamide function can also be obtained in a manner known per se by an amidation reaction of the corresponding mercaptoalkanoic acid or esters thereof. Such a process can be represented by the following reaction scheme:
(DJ- (XH) n + m xH
wherein X, n, m A and D have the same meaning as in the above and Q represents a hydrogen atom or a saturated or unsaturated, straight or branched alkyl radical of 1 to 10 carbon atoms. However, the preparation process described above initiating with a thiolactone or an iminothiolane is faster and does not lead to the formation of side products that occasionally have a very unpleasant odor and contaminate the final product. Reference may be made to the following documents describing hyperbranched polymers and dendrimers in which the terminal group contains an amine function, the content of these documents is incorporated in the present description by reference: US-694, 064; US-4, 507, 66; US-4, 631, 337; US-4, 558, 120; US-4, 568, 737; US-4, 587, 329; O-A-9502008; WO-A-9314147; EP-234408; US-4, 289, 872; US-4,360,646; Proc. Nati Acad. Sci. USA, 8_5, 5409-5413 (1988); O95 / 02008; W093 / 14147; J. Am. Chem. Soc. 117, 9764 (1195); FR-2, 734, 268. Dendrimers containing terminal groups that carry a primary amine function are polyamidoamines such as those sold under the brand name Starburst PAMAM by the company Dendritech.
(block copolymers of ethylene diamine and methyl acrylate). It is also possible to choose polyalkylene polyamine type dendrimers such as, for example, polyethylene imines and polypropylene imines manufactured by the company DSM and described in the patents: WO 93/14147 and WO 95/02008. They may also belong to the polylysine family, as described in U.S. Patent No. 4,360,646. Among the hyperbranched polymers, mention may be made of polyalkylene polyamines such as the polyethyleneimine sold by the company BASF under the trademarks Polymin and Lupasol. They may also consist of hyperbranched polymers and dendrimers containing amine functional groups of a nucleus and generations of base units, monomers or axes of any nature, in which an end group T carrying an amine function has been grafted.
Hyperbranched polymers and dendrimers containing hydroxyl end groups, in particular polymers of the polyester family, are described in the following documents, the content of which is incorporated in the present description by reference: US 4,587,329; WO 93/17060; WO 92/14543; J. Am. Chem. Soc., 113, 4583-4588 (1991); Macro olecules 25_, 4583-4587 (1992); US 5,196,502; US 5,214,122. Preferably, the starting polymer of dendrimers is chosen. After the reaction, the nature of the nucleus and the branches of the starting polymer are not modified. Possibly, as a function of the proportions of the reagents used, some of the starting end groups are not modified. In this way, if a polyamidoamine is used to start with it, which is treated with β-thiobutyrolactone, the process of the invention gives a polyamide containing mercapto-4-butyramide end functions. Starting with a polyalkylene polyamine, the process of the invention gives a polyalkylene polyamine grafted with mercapto-4-butyramide functional groups. When starting with a polyester, the process of the invention gives a polyester containing mercapto-4-butyramide end functions. These novel polymers have reductive properties and can be used in place of conventionally used reducing agents, for example in cosmetic applications, such as, for example, the treatment of nails and hair. In particular, these novel polymers can be used as reducing agents in the permanent waving compositions. Since the polymers according to the invention contain an end function -SH, they can be used as preservatives for protective products which are particularly sensitive to oxidation. They can be used as antioxidants in compositions of any nature, especially in cosmetic or pharmaceutical compositions, for example in hair compositions, such as shampoos, lotions, gels, emulsions or hair sprays, rinsing compositions, to be applied before or after the washing, before or after inking or discoloration, before, during or after permanent waving or straightening of hair, lotions or gels for styling or treatment, lotions or gels for drying by dryer or fixing hair, and compositions for permanent waving, straightening , inked or discolored hair. They can also be used as antioxidants in skin care products or make-up products, such as products for making mascara, eyebrows or skin, such as an epidermal treatment cream, a cream, a lipstick , an eye shadow, a blush, a mask, an eyeliner or nail polish, or cleansing lotions for skin or skin care, creams and milks. The object of the invention is also a composition comprising, on a cosmetically or dermatologically acceptable support, at least one polymer according to the invention. When applied to a support, the polymers according to the invention can form a film resulting from the formation of the intermolecular disulfide bridges, thereby leading to a polymer of the dendrimer or hyperbranched polymer containing end functions -SH. This film can be formed of a few thiol functions, the other functions remain free and are able to have a reductive action.
The use of the polymers according to the invention as antioxidants can be provided directly in solution in the medium to be protected from oxidation, as is common with standard antioxidants such as thioglycolic acid, thiolactic acid or cysteine. If the polymer is insoluble in the medium to be protected from oxidation, it is also possible to envisage fixing it, for example, in the form of a film or a pellet, to the walls or inside the bottle retainer containing the formulation to be protected. In the second case, the dendrimer or hyperbranched polymer according to the invention can also be combined with a small amount of one of the mercaptans usually used as antioxidants, such as, for example, thioglycolic acid, thiolactic acid or cysteine. In this way this combination makes it possible to limit the amount of soluble thiol in the composition to be protected and therefore the usual disadvantages associated with it - odor, color change - while at the same time retaining the remarkable effectiveness. Also in this way the object of the invention is such a combination.
The hyperbranched polymers and dendrimers according to the invention have in particular the advantage of having a much lower odor than the thiols usually used as antioxidants - they are virtually odorless at room temperature. Taking into account their specistructure, the hyperbranched polymers and dendrimers of According to the invention, they penetrate very little into the keratin or the epidermis, and in this way they are not relatively detectable and do not have toxicity problems. Non-limiting examples will be given later for illustration.
Example 1: Dendrimer with a core of ethylenediamine, an axis of ethylenediamine and methyl acrylate, of generation 1, which has 8 surface SH functions. 540 ml of β-thiobutyrolactone (ie 1 equivalent calculated in relation to all functions) are added. primary amine) to 2 grams of an aqueous solution at 55.7 g / 100 g of the dendrimer sold by the company Dendritech under the name PAMAM Starburst with a core of ethylenediamine, generation 1 (8 surface NH2 functions), diluted with 2 ml of water, under an inert atmosphere at room temperature. The medium, which initially heterogeneous, quickly becomes homogeneous (1 hour). After stirring for 48 hours, only traces of β-thiobutyrolactone are found in the medium. The mixture is washed 3 times with 10 ml of diethyl ether and nitrogen is then bubbled through the aqueous phase obtained in this way in order to remove any traces of ether. The aqueous solution obtained in this way is then analyzed by NMR. It is observed that all the initial primary amine functions are in the form The content of the active material of this aqueous phase is 37.71 g / 100 g. The dendrimer obtained in this way is used while it is in aqueous solution. Molar mass of the synthesized product: 2247 g.mol-1
Empirical formula: C9 H? 76N26? 2oS8
Example 2: Dendrimer with a core of ethylenediamine, an axis of ethylenediamine and methyl acrylate, of generation 3, which has 16 surface NH2 functions and 16 superal SH functions. 384 ml of β-thiobutyrolactone (ie 0.5 calculated equivalents) are added. in relation to all primary amine functions) to 4 grams of an aqueous solution at 47.85 g / 100 g of the dendrimer sold by the company Dendritech under the name PAMAM Starburst with a core of ethylenediamine, generation 3 (32 superal NH2 functions) , diluted with 4 ml of water, under an inert atmosphere at room temperature. After the addition, the heterogeneous medium becomes rapidly homogenous (1 hour). After stirring for 20 hours, no more thiobutyrolactone is detected in the medium. The aqueous solution obtained in this way is analyzed by NMR. It is observed that 50% of the initial primary amine functions are in the -NH-CO- (CH2) 3-SH form. The content of the active material of this aqueous phase is 27.75 g / 100 g. The dendrimer obtained in this way is used while it is in aqueous solution. Molar mass of the synthesized product: 8532 g .mol-1 Empirical formula: C366H70 N122O76S16 Example 3: Dendrimer with an ethylenediamine nucleus, an axis of ethylenediamine and methyl acrylate, of generation 1, having 1.6 surface NH2 functions and 6.4 surface SH functions 431 ml of? -thiobutyrolactone (ie 0.8 equivalents calculated in relation to all primary amine functions) are added to 2 grams of an aqueous solution at 55.7 g / 100 g of the dendrimer sold by the company Dendritech under the name PAMAM Starburst with a nucleus of ethylenediamine, generation 1 (8 superficial NH2 functions), diluted with 2 ml of water, under one inert atmosphere at room temperature. The medium, which is initially heterogeneous, quickly becomes homogeneous (1 hour). After stirring for 24 hours, no more are detected -thiobutyrolactone in the medium. The aqueous solution obtained in this way is analyzed by NMR. It is observed that 80% of the initial primary amine functions are in the -NH-CO- (CH2) 3-SH form. The content of the active material of this aqueous phase is 35.99 g / 100 g. The dendrimer obtained in this way is used while it is in aqueous solution. Molar mass of the synthesized product: 2080. 8 g .mol "1 Empirical formula: C87.6Hi66.4N26O? 8.4 S6.4 Example 4: Polyethyleneimine branched polymer with average molecular weight MW = 1200, which has 6.75 SH functions 1 gram of polyethylenimine of average molecular weight PM is diluted = 1200 sold by the company Polysciences in 3 grams of water and then 482 μl of β-thiobutyrolactone (ie 6.75 molar equivalents, calculated based on the average molecular weight of the polymer) is added at room temperature under an inert atmosphere. which is initially heterogeneous, becomes rapidly homogenous (approximately 30 minutes) .After stirring for 2 hours, no more thiobutyrolactone is detected in the medium.The aqueous phase gives a positive reaction after being developed with sodium nitroproside. it observes in this way that the initial primary amine functions are in the form of -NH-CO- (CH2) 3-SH.The content of active material of this aqueous phase is 34.35 g / 100 g. This form is used while it is in aqueous solution. Molar mass of the synthesized product: 1889.6 g.mol "1 Example 5: Branched polyethyleneimine polymer of average molecular weight PM = 2000, having 5.5 SH functions on average per unit 595 μl of? -thiobutyrolactone (ie 5.5 molar equivalents) are added , calculated relative to the monomer) at room temperature to 5 grams of an aqueous solution containing 50% polyethyleneimine of average molecular weight MW = 2000, sold by the company BASF under the name Lupasol G35, under an inert atmosphere at room temperature. The medium, which is initially heterogeneous, becomes rapidly homogenous (approximately 30 minutes) After stirring for 16 hours, no more thiobutyrolactone is detected in the medium.The aqueous phase gives a positive reaction after revealing with nitroproside. It is observed in this way that some of the initial primary amine functions are in the form of -NH-CO- (CH2) 3-SH.The active material content of this phase aqueous is 56.16 g / 100 g. The polymer obtained in this way is used while it is in aqueous solution. Molar mass of the synthesized product: 2561.88 g.mol-1 Example 6: Branched polyethyleneimine polymer of average molecular weight MW = 2000, having 11.09 SH functions on average per unit 12 ml of β-thiobutyrolactone (ie 11.09 molar equivalents) are added , calculated relative to the monomer) at room temperature to 50 grams of an aqueous solution containing 50% polyethyleneimine of average molecular weight MW = 2000, sold by the company BASF under the name Lupasol G35, under an inert atmosphere at room temperature. The medium, which is initially heterogeneous, quickly becomes homogeneous (approximately 30 minutes). After stirring for 16 hours, no more is detected -thiobutyrolactone in the medium. The aqueous phase gives a positive reaction after revealing with sodium nitroproside. It is observed in this way that some of the initial primary amine functions are in the form of -NH-CO- (CH2) 3-SH. This aqueous phase can be diluted with enough water to carry it to 100 ml. The content of active material of this aqueous phase is 39.16 g / 100 ml, that is 1,386 mol. I "1 of thiol Its pH is 9.7 The polymer obtained in this way is used while it is in aqueous solution Molar mass of the synthesized product: 3132.95 g.mol-1 Example 7: Polyethylenimine branched polymer of average molecular weight PM = 2000, which has 1 SH function on average per unit. 432 μl of? -thiobutyrolactone (ie 1 molar equivalent, calculated relative to the monomer) is added at room temperature to 20 grams of an aqueous solution containing 50% polyethyleneimine of weight average MW = 2000, sold by the company BASF under the name Lupasol G35, under an inert atmosphere at room temperature.The medium, which is initially heterogeneous, quickly becomes homogeneous (approximately 30 minutes) .After stirring for 1 hour , no more detected -thiobutyrolactone in the medium.The aqueous phase gives a positive reaction after revealing with sodium nitroproside.It is observed in this way that some of the primary amine functions Niciales are in the form The content of the active material of this aqueous phase is 51.24 g / 100 g. The pH is 11.6. The polymer obtained in this way is used while it is in aqueous solution. Molar mass of the synthesized product: 2102.16 g.mol "1 Example 8: Polyethyleneimine branched polymer of average molecular weight PM = 2000, having 16 SH functions on average per unit 10.4 ml of? -thiobutyrolactone (ie 16 molar equivalents) are added. , calculated relative to the monomer) at room temperature to 30 grams of an aqueous solution containing 50% polyethyleneimine of average molecular weight MW = 2000, sold by the company BASF under the name Lupasol G35, under an inert atmosphere at room temperature. The medium, which is initially heterogeneous, becomes rapidly homogenous (approximately 30 minutes) After stirring for 48 hours, no more thiobutyrolactone is detected in the medium The aqueous phase gives a positive reaction after revealing with nitroproside. It is observed in this way that some of the initial primary amine functions are in the form of -NH-CO- (CH2) 3-SH. Uosa is 64.5 g / 100 g. The polymer obtained in this way is used while it is in aqueous solution. Molar mass of the synthesized product: 3634.56 g.mol-1 Example 9: Polyethyleneimine branched polymer of average molecular weight PM = 2000, having 4 SH functions on average per unit 4.33 ml of? -thiobutyrolactone (ie 4 molar equivalents) are added. , calculated relative to the monomer) at room temperature to 50 grams of an aqueous solution containing 50% polyethyleneimine of average molecular weight MW = 2000, sold by the company BASF under the name Lupasol G35, under an inert atmosphere at room temperature. The medium, which is initially heterogeneous, quickly becomes homogeneous (approximately 30 minutes). After stirring for 4 hours, no more is detected-thiobutyrolactone in the medium. The aqueous phase gives a positive reaction after revealing with sodium nitroproside. It is observed in this way that some of the initial primary amine functions are in the form of -NH-CO- (CH2) 3-SH. This aqueous phase can be diluted with enough water to carry it to 100 ml. The content of the active material of this aqueous phase is 30.11 g / 100 ml, that is to say 0.5 mol. 1- thol. Its pH is 10.3. The polymer obtained in this way is used while it is in aqueous solution. Molar mass of the synthesized product: 2408.64 g.mol-1 Example 10: Branched polyethyleneimine polymer of average molecular weight MW = 2000, having 10 SH functions on average per unit 6.5 ml of β-thiobutyrolactone (ie 10 molar equivalents) are added , calculated relative to the monomer) at room temperature to 30 grams of an aqueous solution containing 50% polyethyleneimine of average molecular weight MW = 2000, sold by the company BASF under the name Lupasol G35, under an inert atmosphere at room temperature. The middle, which is initially heterogeneous, quickly becomes homogeneous (approximately 30 minutes). After stirring for 24 hours, no more is detected-thiobutyrolactone in the medium. The aqueous phase gives a positive reaction after revealing with sodium nitroproside. It is observed in this way that some of the initial primary amine functions are in the form of -NH-CO- (CH2) 3-SH. This aqueous phase can be diluted with enough water to carry it to 100 ml. The content of the active material of this aqueous phase is 22.66 g / 100 ml, that is to say 0.75 moles. I-1 of thiol. Its pH is 9.6. The polymer obtained in this way is used while it is in aqueous solution. Molar mass of the synthesized product: 3021.6 g.mol "1 Example 11: Polyethyleneimine branched polymer of average molecular weight MW = 25,000, which has 50 SH functions on average per unit 12.28 g of water are added, at room temperature, to 12.28 grams of an aqueous solution containing 56% polyethyleneimine of average molecular weight MW = 25,000, sold by the company BASF under the name Lupasol HF, followed, when the medium has once again become homogeneous, by 1.2 ml of β-thiobutyrolactone ( ie 50 molar equivalents calculated in relation to the monomer) under an inert atmosphere at room temperature The medium, which is initially heterogeneous, becomes rapidly homogeneous (approximately 30 minutes) After stirring for 14 hours, no more is detected? -thiobutyrolactone in the medium.The aqueous phase gives a positive reaction after revealing with sodium nitroproside.It is observed in this way that some of the initial primary amine functions are in the form The content of the active material of this aqueous phase is 31.88 g / 100 g. The polymer obtained in this way is used while it is in aqueous solution. Molar mass of the synthesized product: 30,108 g.mol "1 Example 12: Polyethyleneimine branched polymer of average molecular weight MW = 25,000, having 125 SH functions on average per unit 22.43 g of water are added, at room temperature, to 22.43 grams of an aqueous solution containing 56% polyethyleneimine of average molecular weight MW = 25,000, sold by the company BASF under the name Lupasol HF, followed by 5.44 ml of? -thiobutyrolactone (ie 125 molar equivalents calculated relative to the monomer) under an inert atmosphere at room temperature The medium, which is initially heterogeneous, becomes rapidly homogenous (approximately 30 minutes) After stirring for 14 hours, no more is detected -thiobutyrolactone in the medium.The aqueous phase gives a reaction positive after revealing with sodium nitroproside It is observed in this way that some of the initial primary amine functions are in the form of -NH-CO- (CH2) 3-SH. of the active material of this aqueous phase is 38.96 g / 100 g. The polymer obtained in this way is used while it is in aqueous solution. Molar mass of the synthesized product: 37,770 g.mol -1 Example 13: Polyethyleneimine branched polymer of average molecular weight MW = 10,000, having 50 SH functions on average per unit 11.30 g of polyethylenimine at 99% MW average molecular weight are diluted = 10,000, sold by the company Polysciences, with 11.30 ml of water, followed by the addition, at room temperature, of 4.9 ml of β-thiobutyrolactone (ie 50 molar equivalents calculated relative to the monomer) under an inert atmosphere at room temperature . The medium, which is initially heterogeneous, quickly becomes homogeneous (approximately 30 minutes). After stirring for 14 hours, no more is detected -thiobutyrolactone in the medium. The aqueous phase gives a positive reaction after revealing with sodium nitroproside. It is observed in this way that some of the initial primary amine functions are in the form The content of the active material of this aqueous phase is 60.17 g / 100 g. The polymer obtained in this way is used while it is in aqueous solution. Molar mass of the synthesized product: 15, 108 g.mol "1 Example 14: Branched polyethyleneimine polymer of average molecular weight MW = 10,000, having 20 SH functions on average per unit 10.15 g of polyethylenimine at 99% MW average molecular weight MW = 10,000, sold by the Polysciences company, with 10.15 ml of water, followed by the addition, at room temperature, of 1.76 ml of β-thiobutyrolactone (ie 20 molar equivalents calculated relative to the monomer) under an inert atmosphere at room temperature. It is initially heterogeneous, becomes rapidly homogenous (approximately 30 minutes) .After stirring for 14 hours, no more thiobutyrolactone is detected in the medium.The aqueous phase gives a positive reaction after revealing with sodium nitroproside. in this way some of the initial primary amine functions are in the form of -NH-CO- (CH2) 3-SH.The content of the active material of this aqueous phase is 54.63 g / 100 g. In this way it is used while it is in aqueous solution. Molar mass of the synthesized product: 12,043.2 g.mol "1 Example 15: Polyethyleneimine branched polymer of average molecular weight PM = 2000, having 12 SH functions on average per unit 20.78 ml of? -thiobutyrolactone (ie 12 molar equivalents) are added. calculated in relation to the monomer) at room temperature to 80 grams of an aqueous solution containing 50% polyethyleneimine of average molecular weight MW = 2000, sold by the company BASF under the name Lupasol G35, under an inert atmosphere at room temperature. medium, which is initially heterogeneous, becomes rapidly homogenous (approximately 30 minutes) .After stirring for 14 hours, no more thiobutyrolactone is detected in the medium.The aqueous phase gives a positive reaction after revealing with sodium nitroproside. It is observed in this way that some of the initial primary amine functions are in the form of -NH-CO- (CH2) 3-SH.The content of the active material of this phase aqueous is 61.73 g / 100 g. The pH is 10.8. The polymer obtained in this way is used while it is in aqueous solution. Molar mass of the synthesized product: 3225.92 g.mol "1 Example 16: Polyethylene imine branched polymer of average molecular weight PM = 2000, having 6 SH functions on average per unit N-acetylhomocysteine thiolactone powder is added, at room temperature, in a ratio of 1 equivalent per equivalent, to 10 grams of an aqueous solution containing polyethyleneimine at 50% MW average molecular weight = 2000, sold by BASF under the name Lupasol G35, under an inert atmosphere. Initially heterogeneous, it becomes rapidly homogenous.The disappearance of N-acetylhomocysteine thiolactone and the appearance of thiol functions are monitored by thin layer chromatography.When all the N-acetylhomocysteine thiolactone has reacted, an additional N-acetylcholine equivalent is added. acetylhomocysteine thiolactone The addition is stopped after the reaction of 6 equivalents (calculated in relation to the polymer) The very viscous medium It is clear, homogeneous and colorless. The content of the active material of this aqueous phase is 59.64 g / 100 g. The polymer obtained in this way is used while it is in aqueous solution. Molar mass of the synthesized product: 2955 g.mol "1 Example 17: Polyethyleneimine branched polymer of average molecular weight PM = 2000, having 3 SH functions on average per unit 2.39 g of powdered N-acetylhomocysteine thiolactone (i.e. 3 equivalents calculated in relation to the polymer), at room temperature, to 20 grams of an aqueous solution containing polyethyleneimine 50% MW average molecular weight = 2000, sold by the company BASF under the name Lupasol G35, diluted with 10 ml of The medium, which is initially heterogeneous, quickly becomes homogeneous, the disappearance of the N-acetylhomocysteine thiolactone and the appearance of the thiol functions are monitored by thin layer chromatography, after 3 hours at room temperature., the reaction is completed. The medium is clear, homogeneous and colorless and the pH is 10.9. The content of the active material of this aqueous phase is 38.25 g / 100 g. The polymer obtained in this way is used while it is in aqueous solution. Molar mass of the synthesized product: 2477.6 g.mol "1
Example 18: Branched polyethyleneimine polymer of average molecular weight PM = 2000, having 10 SH functions on average per unit 4.43 g of powdered N-acetylcysteine methyl ester (ie 10 equivalents calculated in relation to the polymer) are added, room temperature, to 10 grams of an aqueous solution containing 50% polyethyleneimine of average molecular weight PM = 2000, sold by the company BASF under the name Lupasol G35, diluted with 5 ml of water, under an inert atmosphere. The ester is prepared above according to the usual methods, starting with N-acetylcysteine in methanol in the presence of an acid catalyst at room temperature. The medium, which is initially heterogeneous, quickly becomes homogeneous. The disappearance of the methyl ester and the appearance of the thiol polymer are monitored by thin layer chromatography. After 1 hour at room temperature, the reaction is complete. The medium is clear, homogeneous and very pale yellow, and the pH is 10. The content of the active material of this aqueous phase is 8.63 g / 100 g. The polymer obtained in this way is used while it is in aqueous solution. Molar mass of the synthesized product: 3452.23 g.mol-1 Example 19: Branched polyethyleneimine polymer of average molecular weight PM = 2000, having 5 SH functions on average per unit 2.2 g of N-acetylcysteine methyl ester powder are added ( ie 5 equivalents calculated in relation to the polymer), at room temperature, to 10 grams of an aqueous solution containing 50% polyethyleneimine of average molecular weight MW = 2000, sold by the company BASF under the name Lupasol G35, diluted with 5% by weight. my water, under an inert atmosphere. The medium, which is initially heterogeneous, quickly becomes homogeneous. The disappearance of the methyl ester and the appearance of the thiol polymer are monitored by thin layer chromatography. After 1 hour at room temperature, the reaction is complete. The medium is clear, homogeneous and very pale yellow, and the pH is 10.6. The content of the active material of this aqueous phase is 6.815 g / 100 g. The polymer obtained in this way is used while it is in aqueous solution. Molar mass of the synthesized product: 2726.1 g.mol-1 Example 20: Branched polyethyleneimine polymer of average molecular weight PM = 2000, having 1 SH function on average per unit 221 mg of powdered N-acetylcysteine methyl ester are added ( ie 1 equivalent calculated with respect to the polymer), at room temperature, at 5 grams of an aqueous solution containing 50% polyethyleneimine of average molecular weight MW = 2000, sold by the company BASF under the name Lupasol G35, under one atmosphere inert. The medium, which is initially heterogeneous, quickly becomes homogeneous. The disappearance of the methyl ester and the appearance of the thiol polymer are monitored by thin layer chromatography. After 7 hours at room temperature, the reaction is complete. The medium is clear, homogeneous and very pale yellow. The content of the active material of this aqueous phase is 51.4 g / 100 g. The polymer obtained in this way is used while it is in aqueous solution. Molar mass of the synthesized product: 2145.2 g.mol-1
Example 21: Branched polyethyleneimine polymer of average molecular weight PM = 2000, having 3 SH functions on average per unit 1.76 g of 2,4-thiazolidinedione powder (ie 3 equivalents calculated relative to the polymer) are added, at temperature environment, to 20 grams of an aqueous solution containing polyethyleneimine 50% MW average molecular weight = 2000, sold by the company BASF under the name Lupasol G35, diluted with 5 ml of water, under an inert atmosphere. The medium, which is initially heterogeneous, quickly becomes homogeneous. After 48 hours at room temperature, the reaction is completed. The content of the active material of this aqueous phase is 43.95 g / 100 g. The polymer obtained in this way is used while it is in aqueous solution. Molar mass of the synthesized product: 2351.4 g.mol-1
It is noted that in relation to this date, the best method known to the applicant to carry out the aforementioned invention, is that which is clear from the present description of the invention.
Claims (23)
1. A polymer chosen from hyperbranched polymers and dendrimers, characterized in that it contains functional groups corresponding to formula (I): Y II HS-A- -c- (l) in which: * Y represents an oxygen atom or an NH group, * A represents a linear, branched or cyclic, saturated or unsaturated alkanedi group of 1 to 12 carbon atoms; this alkandiyl group can be optionally interrupted by one or more heteroatoms, such as O or N; this alkandiyl group can be optionally substituted with one of the following amino functions: -NH2, optionally in the form of a salt of an inorganic or organic acid, acylamino: -NH-COR, in which R represents a linear, branched alkyl group or cyclic, saturated or unsaturated of 1 to 10 carbon atoms, carboxylic acid, ester of 1 to 10 carbon atoms; * X represents a nucleophilic group
2. Polymer according to claim 1, characterized in that A represents a radical corresponding to one of formulas (a) to (d) below: -CHR1-CHR2-CHR3- (a) -CHR '^ CHR ^ -CHR' 3-CHR '4- (b) - (CHR '' '1) k- (CHR' '' 2) -CH (C02H) -NH- (d) in which * R1, R2, R3, R'1, R'2, R'3, R'4, R '"t and R"' 2, which may be identical or different, represent: a hydrogen atom, a linear, branched or cyclic, saturated or unsaturated alkyl radical of 1 to 6 carbon atoms, an amino radical -NH2, a. carboxylic acid radical -COOH, an alkylamino radical of 1 to 10 carbon atoms, an acylamino radical of 1 to 10 carbon atoms; * R''1, R''2, R''3 and R''4, which may be identical or different, represent: a hydrogen atom, a linear or branched, saturated or unsaturated alkyl radical of 1 to 4 atoms of carbon, the arrows indicate the positions of the substitutions in the formula (c), * k is an integer, preferably k = 0 or 1.
3. Polymer according to claim 2, characterized in that A = -CH2-CH (C02H) -NH- and Y = 0 or A = - (CH2) 2- (CH3CONH) CH- and Y = 0 or A = - (CH2) ) 3- and Y = O or A = - (CH2) 3- Y = NH.
4. Polymer according to claim 3, characterized in that A is the trimethylene radical: -CH 2 -CH 2 -CH 2 -, and Y = 0.
5. Polymer according to any of the preceding claims, characterized in that X represents either an oxygen atom or a group -NR'-, in which R 'is chosen from a hydrogen atom; a linear or branched, saturated or unsaturated alkyl group of 1 to 6 carbon atoms; a mono- or polyhydroxyalkyl group, linear or branched, unsaturated saturated with 1 to 6 carbon atoms; an aminoalkyl group of 1 to 6 carbon atoms or a polyalkyleneimine group.
6. Polymer according to claim 5, characterized in that X is selected from an oxygen atom and an NH group.
7. Polymer according to any of claims 1 to 6, characterized in that at least 10%, in numerical terms, of the X groups of the hyperbranched polymer or of the dendrimer are grafted with a functional group: O II HS-CH¿-CH-CHj-C and even more preferably at least 40%.
8. Polymer according to any of claims 1 to 7, characterized in that it belongs to the family of polyamide.
9. Polymer according to any of claims 1 to 7, characterized in that it belongs to the polyalkylene polyamine family.
10. Polymer according to claim 9, characterized in that it is a polyethyleneimine. •eleven.
Polymer according to any of claims 1 to 7, characterized in that it belongs to the polyester family.
12. Polymer according to any of the preceding claims, characterized in that it belongs to the family of the dendrimer.
13. Process for preparing polymers according to any of claims 1 to 12, characterized in that a starting polymer, chosen from hyperbranched polymers and dendrimers in which the end groups or chains contain a nucleophilic function, is reacted with a thiolactone or a iminothiolane according to the reaction scheme: @ - (XH). + MxSr- > . _- (X-? A-SH); m in which represents a dendrimer or a hyperbranched polymer containing n end functions XH, X represents a nucleophilic group, m is an integer m. < _ n and A represents a radical corresponding to one of formulas (a) to (d): -CHR1-CHR2-CHR3- (a) -CHR'1-CHR'2-CHR '3-CHR'4- (b) - (CHR "' ') k- (CHR"') -CH (C02H ) -NH- (d! in which R1, R2, R3, R'1, R'2, R '3, R'4, R' '' 1 and R '' '2, which may be identical or different, represent: a hydrogen atom , a linear or branched, saturated or unsaturated alkyl radical of 1 to 6 carbon atoms, an amino radical -NH2, a carboxylic acid radical -COOH, an alkylamino radical of 1 to 10 carbon atoms; R "1, R" 2, R "3 and R" 4, which may be identical or different, represent: a hydrogen atom, a linear or branched, saturated or unsaturated alkyl radical of 1 to 4 carbon atoms; carbon, the arrows indicating the positions of the substitutions in the formula (c), k is an integer, preferably k = 0 or 1.
14. Process according to claim 13, characterized in that is chosen from procisteine N-acetylhomocysteintiolactone CL-iminothiolane-thiobutyrolactone:
15. Process according to claim 14, characterized in that is? -thiobutyrolactone.
16. Process according to any of claims 13 to 15, characterized in that the reaction to open the thiolactone or iminiothiolane is carried out under an inert atmosphere in an aromatic solvent or an alcohol at a temperature, in the range of 0 ° C to 110 ° C .
17. Process according to any of claims 13 to 15, characterized in that the reaction is carried out in water, in the presence, in stoichiometric proportions, of the starting polymer and the thiolactone or the thiolane, the mixture is brought, under an inert atmosphere, to a temperature in the range from 0 ° C to 110 ° C.
18. Process for preparing polymers according to any of claims 1 to 12, characterized in that the starting polymer, chosen from hyperbranched polymers and dendrimers, in which the end groups or chains contain a nucleophilic function, is reacted with a mercaptoalkanoic acid or an ester of mercaptoalkanoic acid according to the following reaction scheme: ®D} - (XH) n + m x HS-A-C-O-Q wherein n, m and ID have the same meaning as in claim 13, A and X have the same meaning as in claim 1 and Q represents a hydrogen atom or a saturated or unsaturated, linear or branched alkyl radical of 1 to 10 carbon atoms.
19. The use of a polymer according to any of claims 1 to 12, as a reducing agent.
20. The use of a polymer according to any of claims 1 to 12, as an antioxidant.
21. A composition, characterized in that it comprises, on a cosmetically or dermatologically acceptable support, at least one polymer according to any of claims 1 to 12.
22. The combination of at least one polymer, according to any of claims 1 to 12, with at least one compound selected from thioglycolic acid, thiolactic acid and cysteine.
23. The cosmetic composition, characterized in that it comprises, in a cosmetically acceptable support, a combination according to claim 22.
Applications Claiming Priority (4)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| FR9704085 | 1997-04-03 | ||
| FR9704085A FR2761691B1 (en) | 1997-04-03 | 1997-04-03 | THIOL TERMINAL FUNCTION POLYMERS |
| FR04085 | 1997-04-03 | ||
| PCT/FR1998/000620 WO1998044024A1 (en) | 1997-04-03 | 1998-03-26 | Polymers with thiol terminal function |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| MXPA99008947A true MXPA99008947A (en) | 2000-01-01 |
| MX9908947A MX9908947A (en) | 2000-01-31 |
Family
ID=9505489
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| MX9908947A MX9908947A (en) | 1997-04-03 | 1998-03-26 | POLYMERS WITH A TERMINAL FUNCTION OF TIOL. |
Country Status (15)
| Country | Link |
|---|---|
| US (1) | US6395867B1 (en) |
| EP (1) | EP0971972B1 (en) |
| JP (1) | JP3413212B2 (en) |
| CN (1) | CN1259152A (en) |
| AT (1) | ATE264357T1 (en) |
| AU (1) | AU7052298A (en) |
| BR (1) | BR9815464A (en) |
| CA (1) | CA2284896A1 (en) |
| DE (1) | DE69823177T2 (en) |
| ES (1) | ES2219884T3 (en) |
| FR (1) | FR2761691B1 (en) |
| HU (1) | HUP0002321A2 (en) |
| MX (1) | MX9908947A (en) |
| PL (1) | PL336002A1 (en) |
| WO (1) | WO1998044024A1 (en) |
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| FR2772770B1 (en) | 1997-12-19 | 2000-01-28 | Oreal | NOVEL COMPOUNDS SELECTED AMONG HYPERBRANCHED POLYMERS AND DENDRIMERS HAVING A PARTICULAR GROUPING, METHOD OF PREPARATION, USE AND COMPOSITIONS COMPRISING THE SAME |
| NL1013942C2 (en) * | 1999-12-23 | 2001-06-26 | Dsm Nv | Multifunctional thermal-oxidative stabilizer. |
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| US20050002886A1 (en) * | 2003-05-06 | 2005-01-06 | Michel Philippe | Dithiols comprising at least one amide functional group and their use in transforming the shape of the hair |
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| WO2005105881A1 (en) * | 2004-04-30 | 2005-11-10 | Canon Finetech Inc. | Antioxidants and recording media made by using the same |
| CN101402738B (en) * | 2007-07-23 | 2012-06-06 | 中国科学院成都有机化学有限公司 | Cationic polymer |
| FR2921256B1 (en) * | 2007-09-24 | 2009-12-04 | Oreal | COMPOSITION FOR COLORING KERATINIC FIBERS COMPRISING AT LEAST ONE DIRECT DYE WITH DISULFURE / THIOL FUNCTION AND AT LEAST ONE THIOL-FUNCTIONAL POLYMER AND PROCESS USING THE COMPOSITION |
| WO2009049746A2 (en) * | 2007-10-09 | 2009-04-23 | Green River Polymers Forschungs- Und Entwicklungs Gmbh | Hair-treatment composition based on sulphur-containing anionogenic polymers |
| FR2929281B1 (en) | 2008-03-28 | 2011-03-11 | Polyrise | MODIFICATION OF THE SURFACE CHEMISTRY OF MACROMOLECULAR SPECIES IN THE PRESENCE OF A CONJUGATED GUANIDINE |
| US8901263B2 (en) * | 2008-12-11 | 2014-12-02 | 3M Innovative Properties Company | Amide-linked perfluoropolyether thiol compounds and processes for their preparation and use |
| US8895032B2 (en) | 2009-03-27 | 2014-11-25 | Central Michigan University | Dendritic nano-antioxidants |
| FR3039765B1 (en) | 2015-08-07 | 2018-08-24 | Oreal | COSMETIC PROCESS FOR TREATING KERATINIC MATERIALS |
| WO2017036504A1 (en) | 2015-08-31 | 2017-03-09 | L'oreal | Wrinkle-reducing cosmetic method |
| CN112011062B (en) * | 2019-05-29 | 2022-06-24 | 彤程新材料集团股份有限公司 | Non-silane polymer coupling agent, preparation method and vulcanizable rubber composition |
| CN112724403B (en) * | 2019-10-14 | 2022-10-04 | 中国科学院上海有机化学研究所 | Poly (gamma-thiobutyrolactone) and preparation method thereof |
| US11242609B2 (en) | 2019-10-15 | 2022-02-08 | Rohm and Hass Electronic Materials LLC | Acidic aqueous silver-nickel alloy electroplating compositions and methods |
| FR3109313B1 (en) | 2020-04-15 | 2022-11-25 | Oreal | METHOD FOR THE TREATMENT OF KERATIN MATERIALS USING AN ACRYLIC POLYMER OF ANHYDRIDE IN OILY DISPERSION AND A HYDROXYL AND/OR THIOLE COMPOUND |
| FR3111904B1 (en) | 2020-06-30 | 2022-10-21 | Oreal | Bioink for bioprinting of an invaginated dermal-epidermal junction model |
| JP7213391B2 (en) * | 2020-11-13 | 2023-01-26 | 三井化学株式会社 | Polythiol composition, polymerizable composition, resin, molding, optical material and lens |
| WO2022128901A1 (en) | 2020-12-17 | 2022-06-23 | L'oreal | Process for dyeing keratin fibres using two different compounds that are capable of forming covalent bonds together and also a particular metal salt or a salt of a metal belonging to the rare-earth metal group or a particular organometallic compound |
| FR3117850A1 (en) | 2020-12-17 | 2022-06-24 | L'oreal | Process for dyeing keratin fibers using two distinct compounds capable of forming covalent bonds together and a metal salt belonging to the rare earth group |
| FR3117849A1 (en) | 2020-12-17 | 2022-06-24 | L'oreal | Process for dyeing keratinous fibers using two distinct compounds capable of forming covalent bonds together as well as a particular metal salt |
| FR3117851A1 (en) | 2020-12-17 | 2022-06-24 | L'oreal | Process for dyeing keratin fibers using two distinct compounds capable of forming covalent bonds together as well as a particular organometallic compound |
| FR3117856B1 (en) | 2020-12-23 | 2024-05-10 | Oreal | Cosmetic composition comprising a block copolymer based on acetoacetate functions |
| FR3117854B1 (en) | 2020-12-23 | 2024-03-15 | Oreal | Cosmetic composition comprising polymeric particles based on acetoacetate functions |
| FR3117852B1 (en) | 2020-12-23 | 2023-06-23 | Oreal | Cosmetic composition comprising a copolymer based on acetoacetate functions |
| WO2022136110A1 (en) | 2020-12-23 | 2022-06-30 | L'oreal | Cosmetic composition comprising polymer particles based on acetoacetate functions |
| WO2022136114A1 (en) | 2020-12-23 | 2022-06-30 | L'oreal | Aqueous dispersion of a specific copolymer, and cosmetic uses thereof |
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| FR3130559A1 (en) | 2021-12-17 | 2023-06-23 | L'oreal | Process for dyeing keratin fibers using a (co)polymer based on acetoacetate functions, a crosslinking agent, a coloring agent and a metal compound |
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-
1997
- 1997-04-03 FR FR9704085A patent/FR2761691B1/en not_active Expired - Fee Related
-
1998
- 1998-03-26 WO PCT/FR1998/000620 patent/WO1998044024A1/en active IP Right Grant
- 1998-03-26 CA CA002284896A patent/CA2284896A1/en not_active Abandoned
- 1998-03-26 ES ES98917248T patent/ES2219884T3/en not_active Expired - Lifetime
- 1998-03-26 JP JP54123498A patent/JP3413212B2/en not_active Expired - Fee Related
- 1998-03-26 AU AU70522/98A patent/AU7052298A/en not_active Abandoned
- 1998-03-26 HU HU0002321A patent/HUP0002321A2/en unknown
- 1998-03-26 MX MX9908947A patent/MX9908947A/en unknown
- 1998-03-26 EP EP98917248A patent/EP0971972B1/en not_active Expired - Lifetime
- 1998-03-26 AT AT98917248T patent/ATE264357T1/en not_active IP Right Cessation
- 1998-03-26 CN CN98805803A patent/CN1259152A/en active Pending
- 1998-03-26 PL PL98336002A patent/PL336002A1/en unknown
- 1998-03-26 US US09/402,201 patent/US6395867B1/en not_active Expired - Fee Related
- 1998-03-26 DE DE69823177T patent/DE69823177T2/en not_active Expired - Fee Related
- 1998-03-26 BR BR9815464-8A patent/BR9815464A/en not_active IP Right Cessation
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