CN1133684C - Polysiloxane copolymer with side quarternary ammonium group and its preparation - Google Patents
Polysiloxane copolymer with side quarternary ammonium group and its preparation Download PDFInfo
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- CN1133684C CN1133684C CNB99111454XA CN99111454A CN1133684C CN 1133684 C CN1133684 C CN 1133684C CN B99111454X A CNB99111454X A CN B99111454XA CN 99111454 A CN99111454 A CN 99111454A CN 1133684 C CN1133684 C CN 1133684C
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- polysiloxane copolymer
- band
- quaternary ammonium
- chloropropyl
- group
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Abstract
The present invention relates to a polysiloxane copolymer with side quarternary ammonium groups, which is a polysiloxane copolymer with quarternary ammonium groups of which the Si-C key is connected with a main chain. The polysiloxane copolymer is prepared in such a manner that the polysiloxane copolymer with gamma-halogeno-propyl side groups is mixed with trialkylamine in a polar solvent, and then the polysiloxane copolymer with gamma-halogeno-propyl side groups and the trialkylamine carry out reaction at the temperature of 100 to 110 DEG C for 40 to 96 hours. The polysiloxane copolymer with side quarternary ammonium groups of the present invention has superior hydrolytic stability, and not only can be used as a finishing agent for fabric and fibre, but also can be used as a modifying agent for organic resin.
Description
The present invention relates to a kind of polysiloxane copolymer with quaternary ammonium lateral group, particularly in a kind of pendant quaternary ammonium groups between the Siliciumatom on N atom and the silicon-oxygen backbone with-CH
2CH
2CH
2-polysiloxane copolymer of being connected and preparation method thereof.
The polysiloxane copolymer that has quaternary ammonium lateral group is known.As at United States Patent (USP) 3,278, the high-molecular weight polysiloxane copolymer of one class band quaternary ammonium lateral group is provided in 465, this analog copolymer is by the polysiloxane copolymer of band silicon hydrogen side group and the alcohol of band tertiary amine groups, dehydrogenation reaction takes place in the presence of catalyzer, and resulting polymers carries out quaterisation with haloalkane again and prepares.Wherein, quaternary ammonium lateral group links to each other with Siliciumatom on the main chain with-Si-O-C-key, because-existence of Si-O-C-key, the hydrolysis less stable of this class polysiloxane copolymer.
At United States Patent (USP) 3,402, in 191, by the polydimethylsiloxane of siliceous hydrogen base and the lower molecular weight polydimethylsiloxane of the addition reaction of silicon with hydrogen anamorphic zone pendant tertiary amine group between vinyloxy group or the allyloxy tertiary amine, carry out quaterisation by the latter and haloalkane again and prepare, wherein on the N of quaternary ammonium lateral group atom and the main chain between the Siliciumatom with-CH
2-O-CH
2-CH
2-key is connected.Because it is special that raw materials used vinyloxy group or allyloxy tertiary amine need, complex process, price is higher, and haloalkane is also more expensive in addition, so this method is not a good method that is suitable for the polysiloxane of industrialized preparation band quaternary ammonium lateral group.
At United States Patent (USP) 4,895, narrated the multipolymer of the high-molecular weight polysiloxane of a class band quaternary ammonium lateral group in 964, this analog copolymer is that the Amine from Tertiary Amine Hydrochloride by the epoxy group(ing) of the polysiloxane copolymer of band oxygen side group and equivalent is that catalyzer carries out quaterisation and prepares with the small-amount free tertiary amine.Linking group on Siliciumatom on this analog copolymer main chain and the quaternary ammonium lateral group between the N atom is-(CH
2)
3-O-CH
2-CH (OH)-CH
2-.The synthesis step of polysiloxane copolymer as the raw band epoxy side group of this analog copolymer of preparation is more, the technology more complicated, and cost is higher.
The present invention has overcome shortcomings such as the existing stability to hydrolysis of polysiloxane copolymer of existing band quaternary ammonium lateral group is poor, complicated process of preparation, and high-molecular weight polysiloxane copolymer of the good band quaternary ammonium lateral group of a class stability to hydrolysis and preparation method thereof is provided.
The molecular structure of the polysiloxane copolymer of band quaternary ammonium lateral group of the present invention is shown below:
In the formula, n=10-500, n/m=1-75 is preferably 2-35; X
-Be Cl
-, Br
-Or l
-R
1And R
2Be alkyl, be preferably methyl with 1-4 C atom; R
3Be selected from the alkyl of 1-18 carbon atom; The alkaryl of 6-8 carbon such as R
4C
6H
4-, R
4Be H, CH
3Or C
2H
5Deng; Aralkyl such as R
5C
6H
4(CH
2)
a-, a is 1 or 2; R
5Be H or CH
3Or hydroxyalkyl such as HO (CH
2)
b-, b is the integer of 1-4.In addition, R
1And R
2Perhaps R
1, R
2And R
3Also can connect into heterocycle with the N atom.Wherein, n=50-500, n/m=2-35; R
1With R
2Be methyl; R
3Be benzyl, phenyl, hydroxyethyl; X
-Be Cl
-Best.
The polysiloxane copolymer of band quaternary ammonium lateral group of the present invention is that polysiloxane by band γ-halopropyl side group is that the mol ratio of 1-6 carry out quaterisation prepare with tertiary amine by N/X in 70-130 ℃ in the presence of polar solvent.
The polysiloxane of above-mentioned band γ-halopropyl side group has structure as follows:
In the formula, n=10-500, n/m=1-75 is preferably 2-35; X is halogen atoms such as Cl, Br and I.When X is Cl, be the polysiloxane copolymer of band chloropropyl side group with structure as follows;
N=50-500 in the formula, n/m=2-35.Table 1 has been listed has as above several polysiloxane copolymers of structure.The structure of the polysiloxane copolymer of table 1 γ-chloro propyl group side group
Structure
Polymkeric substance cl content (wt%) (element branch
N m analyses)
I 88 10 4.37
II 178 20 4.42
III 45.5 2.5 2.29
IV 483 15 1.38
V 134 64 12.1
Above-mentioned tertiary amine has structure as follows:
In the formula, R
1And R
2Be alkyl, be preferably methyl, R with 1-4 C atom
3The alkyl, alkaryl that is selected from the 1-18 carbon atom is as-C
6H
4R
4, R
4Be H, CH
3Or C
2H
5Aralkyl is as-(CH
2)
a-C
6H
4R
5, a is 1 or 2, R
5Be H or CH
3Or hydroxyalkyl is as-(CH
2)
b-OH, b are the integer of 1-4.In addition, R
1And R
2Perhaps R
1, R
2And R
3Also can connect into the heterocycle tertiary amine with the N atom.R wherein
1With R
2Be methyl; R
3For benzyl, phenyl, hydroxyethyl are best.
The tertiary amine that the present invention is suitable for comprises pentahydro-pyridine that triethylamine, dimethyl lauryl amine, dimethylethanolamine, dimethyl benzyl amine, xylidine, pyridine, N-methylpyrrole and N alkyl replace or Pyrrolidine etc.
This reaction does not need catalyzer, is necessary but be to use polar solvent solubilizing reaction thing, and the solvent that is suitable for is N, dinethylformamide, propyl carbinol and acetonitrile etc., or the mixed solvent of being made up of them.Required quantity of solvent has no particular limits, and is generally 0.25-2 times of reactant gross weight.When making solvent with propyl carbinol, its consumption for the polysiloxane copolymer weight of band chloropropyl side group 0.5-2 doubly; When using N, when dinethylformamide was made solvent, its consumption was 1 times of the polysiloxane copolymer weight of band chloropropyl side group; When using N, when dinethylformamide and propyl carbinol were formed mixed solvent, the two weight ratio did not have special restriction, and preferable scope is 0.5-2, and its consumption is 1 times of the polysiloxane copolymer weight of band chloropropyl side group.
This reaction is carried out in 70-130 ℃ of temperature range usually.Temperature is low excessively, and speed of response is too slow; Temperature surpasses 130 ℃, will cause quaternary ammonium compound to begin thermolysis.So temperature of reaction is preferably in 100-110 ℃.The mol ratio of the N/X of reactant can change in from 1 to 6 bigger scope.The suitable excessive speed that will accelerate quaterisation of tertiary amine helps the complete of quaterisation.The time of quaterisation has no particular limits, can 40-96 hour in a big way in change to guarantee quaterisation complete.
Reaction is generally carried out under normal pressure and in the inert atmosphere, but when raw material is low-boiling compound, reaction need be carried out adding to depress.
The reinforced order of quaterisation is without particular limitation, general earlier that reactant and solvent is even, be warming up to temperature of reaction and react, also can be earlier that a kind of reactant and solvent is even, be warming up to temperature of reaction, under agitation drip another kind of reactant and react.
The purifying of quaterisation product adopts usually under reduced pressure and carries out except that the low-molecular material that desolvates with excessive.
Polysiloxane copolymer as the band γ-halogen propyl group side group of quaterisation main raw material is that people are known, can adopt the equilibration reaction under acid or base catalysis to prepare, and the halogen content of product is measured by elemental microanalysis method.
By the polysiloxane copolymer of band quaternary ammonium lateral group provided by the invention, owing to be connected to the divalence propyl group between N atom on the quaternary ammonium group and the Siliciumatom, so have good hydrolysis stability.
Prepare the method that side chain has the polysiloxane copolymer of quaternary ammonium group by polysiloxane copolymer and the reactive tertiary amine by band γ-halopropyl side group provided by the invention, having reaction raw materials is easy to get, low price, quaterisation is simple, the characteristics of no side reaction, the quaternization degree of product can be up to 100%.
The polysiloxane copolymer of band quaternary ammonium lateral group of the present invention can be used for the soft smooth and antistatic finish of fabric, also can be used as the nursing agent and the static inhibitor of hair, can also be as the properties-correcting agent of organic resin, in order to reduce frictional coefficient.The polysiloxane copolymer that has specific quaternary ammonium lateral group structure also can be used as the antibacterial and mouldproof finishing composition of fiber and fabric.
With embodiment the present invention is described below.
Embodiment 1
In container, add 80.2 polydimethylsiloxanes (containing chloropropyl 0.1mol), 40.5 that restrain band chloropropyl and restrain N with aforementioned structure (I), the propyl carbinol of N-dimethyl benzyl amine (0.3mol) and reactant gross weight 50%, be warming up to 102 ℃ after the stirring and dissolving under nitrogen atmosphere, reaction is 60 hours under this temperature.Remove solvent and excessive tertiary amine under reduced pressure, obtain the paste product.
1It is 89% that HNMR spectrum records the chloropropyl quaternization degree
Embodiment 2
Except that propyl carbinol being changed into a times of reactant gross weight, all the other obtain the paste product at last with embodiment 1,
1It is 69% that HNMR spectrum records the chloropropyl quaternization degree.
Embodiment 3
Except that propyl carbinol being changed into the twice of reactant gross weight, all the other obtain faint yellow paste product at last with embodiment 1,
1It is 60% that HNMR spectrum records the chloropropyl quaternization degree.
Embodiment 4
Except that the propyl carbinol/dimethyl formamide mixed solvent (both weight ratios are 1: 1 in the mixed solvent) with weight such as the propyl carbinol among the embodiment 2 change into, all the other obtain paste at last with embodiment 2,
1It is 76% that HNMR spectrum records the chloropropyl quaternization degree.
Embodiment 5
The weight ratio of two kinds of solvents changes into 1: 2 in the propyl carbinol/dimethyl formamide mixed solvent that will adopt among the embodiment 4, and all the other obtain the paste product at last with embodiment 2,
1It is 85% that HNMR spectrum records the chloropropyl quaternization degree.Embodiment 6
Except that the dimethyl formamide with weight such as the propyl carbinol among the embodiment 2 change into, all the other obtain the paste product at last with embodiment 2,
1It is 50% that HNMR spectrum records the chloropropyl quaternization degree.
Embodiment 7
Remove the N among the embodiment 1, the N-dimethyl benzyl amine changes 81.0 grams (0.6mol) into, and propyl carbinol changes into outside a times of reactant gross weight, and all the other obtain the paste product at last with embodiment 1,
1It is 100% that HNMR spectrum records the chloropropyl quaternization degree.
Embodiment 8
Remove N, N-methyl-benzyl amine consumption changes 13.5 grams (0.1mol) into, and propyl carbinol changes into outside a times of reactant gross weight, and all the other obtain paste at last with embodiment 1,
1It is 44% that HNMR spectrum records the chloropropyl quaternization degree.
Embodiment 9
The polydimethylsiloxane (containing chloropropyl 0.02mol) that in container, adds the band chloropropyl of 50.6 gram said structures (IV), 16.2 the N of gram (0.12mol), the propyl carbinol that N-dimethyl benzyl amine and reactant gross weight are one times, be warming up to 110C after the stirring and dissolving under nitrogen atmosphere, reaction is 40 hours under this temperature.Under reduced pressure except that desolvating and crossing quantity tertiary amine, get yellow paste product then,
1It is 95% that HNMR spectrum records the chloropropyl quaternization degree.
Embodiment 10
Polydimethylsiloxane 38.1 grams (containing chloropropyl 0.13mol) at the band chloropropyl that in container, adds said structure (V), N, the propyl carbinol of accelerine 47.2 grams (0.39mol) and reactant gross weight 50%, be warming up to 100 ℃ after the stirring and dissolving under nitrogen atmosphere, reaction is 96 hours under this temperature.Under reduced pressure remove quantity tertiary amine and solvent then, got yellow paste product,
1It is 100% that HNMR spectrum records the chloropropyl quaternization degree.Embodiment 11
In container, add 73.0 polydimethylsiloxanes (containing chloropropyl 0.047mol), 8.4 that restrain band chloropropyl and restrain N with aforementioned structure (III), 50% propyl carbinol of N-dimethylethanolamine (0.094mol) and reactant gross weight, be warming up to 102 ℃ after the stirring and dissolving under nitrogen atmosphere, reaction is 60 hours under this temperature.Remove propyl carbinol and excessive tertiary amine at last under reduced pressure, obtain the paste product.
1It is 85% that HNMR spectrum records the chloropropyl quaternization degree.Comparative example 1
Except no propyl carbinol, all the other obtain milky white liquid at last with embodiment 1,
1It is 11% that HNMR spectrum records the chloropropyl quaternization degree.Comparative example 2
Except temperature of reaction being changed into 55 ℃, all the other obtain colourless transparent liquid at last with embodiment 2,
1It is 2% that HNMR spectrum records the chloropropyl quaternization degree.
Claims (5)
1 one kinds of polysiloxane copolymers with quaternary ammonium lateral group is characterized in that the structural formula of described multipolymer is:
In the formula, n=50-500, n/m=2-35; R
1With R
2Be methyl; R
3Be benzyl, phenyl, hydroxyethyl; X
-Be Cl
-
The preparation method of 2 a kind of polysiloxane copolymers with quaternary ammonium lateral group according to claim 1 is characterized in that with structural formula being
In the formula, n=50-500, n/m=2-35, the polysiloxane copolymer of band chloropropyl side group and tertiary amine be the ratio of 1-6 in the mol ratio of N/Cl, be blended in propyl carbinol or N, in dinethylformamide or the mixed solvent of the two, 100-110 ℃ of reaction 40-96 hour, obtain polysiloxane copolymer with quaternary ammonium lateral group
Above-mentioned tertiary amine is
R in the formula
1With R
2Be methyl, R
3Be benzyl, phenyl, hydroxyethyl.
The preparation method of the polysiloxane copolymer of 3 band quaternary ammonium lateral groups according to claim 2, it is characterized in that described propyl carbinol consumption for the 0.5-2 of the polysiloxane copolymer weight of band chloropropyl side group doubly.
The preparation method of the polysiloxane copolymer of 4 band quaternary ammonium lateral groups according to claim 2 is characterized in that described N, and the dinethylformamide consumption is 1 times of the polysiloxane copolymer weight of band chloropropyl side group.
The preparation method of the polysiloxane copolymer of 5 band quaternary ammonium lateral groups according to claim 2, it is characterized in that described N, dinethylformamide and propyl carbinol be by weight being mixed solvent that 0.5-2 formed, and its consumption is 1 times of the polysiloxane copolymer weight of band chloropropyl side group.
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB99111454XA CN1133684C (en) | 1999-08-16 | 1999-08-16 | Polysiloxane copolymer with side quarternary ammonium group and its preparation |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB99111454XA CN1133684C (en) | 1999-08-16 | 1999-08-16 | Polysiloxane copolymer with side quarternary ammonium group and its preparation |
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| CN1133684C true CN1133684C (en) | 2004-01-07 |
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Families Citing this family (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6482969B1 (en) * | 2001-10-24 | 2002-11-19 | Dow Corning Corporation | Silicon based quaternary ammonium functional compositions and methods for making them |
| DE102005040323A1 (en) * | 2005-08-25 | 2007-03-15 | Wacker Chemie Ag | Organopolysiloxanes and a process for their preparation |
| DE102007047863A1 (en) * | 2007-11-26 | 2009-05-28 | Wacker Chemie Ag | Quaternary ammonium organopolysiloxanes, their preparation and use |
| CN102875814B (en) * | 2012-09-19 | 2016-02-03 | 光景生物科技(苏州)有限公司 | Polysiloxane and preparation method, purposes and the sterilant containing this polysiloxane |
| CN108276580B (en) * | 2018-02-02 | 2021-02-02 | 四川理工学院 | Permanent antistatic MQ resin and preparation method thereof |
| CN108586751A (en) * | 2018-05-16 | 2018-09-28 | 山东交通学院 | A kind of ethenyl blocking polysiloxanes containing quaternary ammonium salt and its synthesis and the application in preparing intrinsic quaternary antibacterial silicon rubber |
| CN111925527B (en) * | 2020-08-21 | 2022-05-24 | 滨州医学院 | Long-chain alkyl grafted quaternized silicone and preparation method and application thereof |
| CN111939307B (en) * | 2020-08-21 | 2022-05-24 | 滨州医学院 | Medical composite nanofiber dressing as well as preparation method and application thereof |
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