CN1224729A - Chemical graft process for preparing pyridine salt polymer as antiseptic material - Google Patents

Abstract

The present invention relates to a preparation method of functional polymer material, in particular, it relates to a chemical grafting method for preparing pyridine salt type polymer antibiotic material. Said method includes solid phase and solution chemical grafting processes, combines surface of polymer matrix with function-group that has antibiotic activity by chemical bond, via preparation and quaternarization reaction of chemical grafting stuff to obtain the polymer antibiotic material containing pyridine salt. The antibiotic material possesses well function, low cost, satisfactory performance in mechanical kinetics and processing and is easy to industrialize.

Description

The chemical graft process of preparation antiseptic material of pyridine salt type polymer

The present invention relates to the preparation method of functional high molecule material, be meant that especially a kind of employing chemical graft process prepares antiseptic material of pyridine salt type polymer.

The polymkeric substance antiseptic-germicide is because its steady chemical structure, non-volatile, the skin that is difficult to permeate humans and animals, and higher antimicrobial efficiency and processing safety etc. preferably, become brand-new developing direction in the anti-biotic material research field in recent years.Contain the antiseptic-germicide of pyridinium salt group on macromolecular main chain, though have antibiotic resistance performance, cost is higher, and as a kind of material, its workability, mechanical mechanics property all have certain limitation, are difficult to satisfy some application requiring.At " polymer science progress " magazine 1992 17 phase P1～34 page Kawabata by Japan (the river end becomes refined) a kind of pyridine salt type polymkeric substance is disclosed to the seizure effect of microorganism and virus and in the application aspect biological and the water purification, it adopts pickling process, with the non-woven fabrics is the method that matrix makes the polymkeric substance anti-biotic material, its specific practice is: the solution dipping-drying of hydrophilic non-woven fabrics being put into the pyridinium salt resin, and then dipping-dry again, repeated multiple times makes the resin-carried antibiotic polymer material that makes microorganism in the effective filtering water on non-woven fabrics of pyridinium salt.When the content that uses 5 layers of pyridinium salt resin filters intestinal bacteria (Ecoli) as the anti-biotic material of 0.09mmol/g, when initial bacterium liquid (preparing with sterile saline) concentration is 10 ⁶Under the condition of cells/ml, the degerming rate is 94%; When using 15 layers of anti-biotic material, the degerming rate is 99.93%.Yet this law prices of raw and semifnished materials costliness is difficult to industrial application in China; And the matrix of the polymkeric substance anti-biotic material that obtains of pickling process and to contain between the polymkeric substance of functional group be a kind of avidity effect, in conjunction with insecure.Therefore, the antibiotic security of this anti-biotic material with immersion process for preparing and persistence all can not get guaranteeing.

The objective of the invention is to overcome the deficiencies in the prior art part, provide a kind of anti-microbial property good, with low cost, mechanical mechanics property and processing characteristics are good, be easy to industrialization and have the preparation method of the antiseptic material of pyridine salt type polymer of broad prospect of application, to satisfy requirement of actual application.

The chemical graft process of preparation antiseptic material of pyridine salt type polymer is characterized in that adopting solid state chemistry grafted method, makes the functional group with anti-microbial activity be combined in the polymer-based carbon surface by chemical bonded refractory, and its step and processing condition are as follows:

Each component is a benchmark with polypropylene (PP) non-woven fabrics weight part

Step 1: the preparation of chemical graft thing

(1) preparation of emulsion

Dibenzoyl peroxide (BPO) 0.5～5 weight part, interfacial agents 8～20 weight parts and nonionogenic tenside 1～5 weight part and deionized water are mixed with 1000 weight part emulsions, interfacial agents nail benzene, chlorobenzene or dimethylbenzene, nonionogenic tenside refers to tween-80 or polyvinyl alcohol;

(2) chemical initiation grafting reaction

With specification is 27～60g/m ²Polypropylene (PP) non-woven fabrics 100 weight parts, 4-vinylpridine (4VP) 20～150 weight parts, emulsion 1000 weight parts in Vinylstyrene (DVB) 0～10 weight part and the above-mentioned steps one (1) place there-necked flask simultaneously, and letting nitrogen in and deoxidizing, reacted 5～7 hours down at 80～95 ℃, unreacted monomer and homopolymer are fallen in extracting again, promptly get the grafts that contains 4VP;

Step 2: the quaterisation of grafts

At first that step 1 is the prepared grafts that contains 4-vinylpridine (4VP) the abundant swelling of capacity ethanol, the halohydrocarbon that adds excessive 100% (weight with the material of 4VP in the grafts is benchmark) then, and letting nitrogen in and deoxidizing, reacted 6～8 hours down at 70～80 ℃, promptly get the polymkeric substance anti-biotic material that contains the pyridine salt type grafts.

The another kind of preparation method of preparation antiseptic material of pyridine salt type polymer is a solution chemistry grafting method, and its step and processing condition are as follows:

Step 1: the preparation of chemical graft thing

With 4-vinylpridine (4VP) 20-200 weight part, toluene 400～550 weight parts, Vinylstyrene (DVB) 0～30 weight part, BPO3～12 weight parts are made into reaction solution, are 27～60g/m with specification more earlier ²Polypropylene (PP) non-woven fabrics 100 weight parts place reaction solution fully to take out behind the dipping, put into there-necked flask, fill the nitrogen deoxygenation then, and after reacting 3～5 hours under 80～95 ℃, unreacted monomer and homopolymer are fallen in extracting, promptly get the grafts that contains 4-vinylpridine (4VP);

Step 2: the quaterisation of grafts

With above-mentioned solid state chemistry grafting method.

The present invention compared with prior art has following distinguishing feature:

1, adopt the anti-biotic material of the method preparation of chemical graft to have good antibiotic security and persistence, and prior art adopt the prepared anti-biotic material of dipping method firm inadequately owing to matrix combines with functional group, can't guarantee its antibiotic safety and persistence.

2, the anti-microbial property of gained anti-biotic material is apparently higher than the bibliographical information value, and the anti-biotic material that Kawabata is prepared is when initial bacterial concentration is 10 ⁶During cells/ml, when adopting 5 layers of anti-biotic material, be 94% to the degerming rate of Ecocli, when adopting 15 anti-biotic material layers, the degerming rate is 99.93%.And be the sample of 0.23mmol/g with chemical graft process gained functional group content of the present invention, adopting intestinal bacteria (Ecocli) is bacterial detection, when initial bacterial concentration is 10 ⁶Cells/ml, when adopting 1 layer of anti-biotic material, the degerming rate is 92.81%, when adopting 10 layers of anti-biotic material, the degerming rate is 99.99%.And the higher sample of other pyridinium salt content, its degerming rate is higher, but their anti-microbial property reference table 3.

3, adopt the PP non-woven fabrics cheap, that mechanical property is very excellent as matrix,, reduced cost, improved the mechanical property of material to overcome the expensive shortcomings of hydrophilic non-woven such as cellulose acetate and nitrocellulose.

4, this anti-biotic material can overcome the mechanical property of " intrinsic " polymkeric substance antiseptic-germicide and the shortcoming of poor processability.

5, mainly be present in polymer surfaces owing to have the functional group of anti-microbial activity, compare with " intrinsic " polymkeric substance antiseptic-germicide like this, both significantly reduced the consumption of functional group, made full use of surperficial functional group again, and improved antimicrobial efficiency, reduced cost.

6, can improve anti-microbial property effectively by the lamination number that increases anti-biotic material, thus applied widely.

7, certain having of degree of crosslinking is beneficial to the formation porosity in the contained functional group of anti-biotic material, thus the inhibition when reducing functional group to water filtration.

8, the antibiotic polymer material of this law preparation, wide application, except to Ecoli effectively, also all effective to streptococcus aureus, mould, fungi, phage and poliovirus etc.

Embodiment 1～6:

With polypropylene (PP) non-woven fabrics is benchmark, by weight.

Press proportioning shown in the table 1 and processing condition, go through following steps and realize solid state chemistry grafting method:

Step 1: the preparation of chemical graft thing

(1) preparation of emulsion:

BPO, interfacial agents, nonionogenic tenside and deionized water are made into 1000 parts of emulsions;

(2) chemical initiation grafting reaction

In there-necked flask, add 1000 parts of polypropylene (PP) non-woven fabrics, 4VP, DVB and the above-mentioned emulsions that is made into, after letting nitrogen in and deoxidizing, the reaction, unreacted monomer and homopolymer are fallen in extracting, and promptly getting monomer or mix monomer percentage of grafting and 4VP content is the grafts shown in the table 1.

The method of calculation of percentage of grafting are as follows in the table 1:

W ₀The quality of-PP non-woven fabrics

W ₁Quality after the grafting of-PP non-woven fabrics

As embodiment 1

(wherein the percentage of grafting of 4VP is 11.0%, and the percentage of grafting of DVB is 2.3%.)

Table 1

As embodiment 1

(molecular weight of 4VP is 105.14)

Step 2:

Grafts with the abundant swelling of ethanol, is added the halohydrocarbon of excessive 100% (amount of substance with 4VP in the grafts is a benchmark), under nitrogen protection, after the reaction, obtain the anti-biotic material that quaternization degree is as shown in table 1, pyridinium salt content is as shown in table 3.This anti-biotic material is removed intestinal bacteria (Ecoli) in anhydrating with general filtering method, and its degerming rate is as shown in table 3.

The method of calculation of the pyridinium salt content of anti-biotic material are as follows in the table 3:

As anti-biotic material among the embodiment 1 pyridinium salt content $=\frac{11.0\×94.3\%/105.14}{100+2.3+11.0\×94.3\%\×(171.04+105.14)/105.14+11.0\×(1-94.3\%)}\×{10}^3\mathrm{mmol}/g$

=0.76mmol/g

(molecular weight of cylite is 171.04).

Embodiment 7～14

Press proportioning shown in the table 2 and processing condition, go through following steps; Realize solution chemistry grafting method:

Step 1: the preparation of chemical graft thing

Earlier 4VP, toluene, DVB and BPO are made into reaction solution by proportioning, again polypropylene (PP) non-woven fabrics 100 weight parts are placed this reaction solution fully to take out behind the dipping, put into there-necked flask, after filling the nitrogen deoxygenation, react at a certain temperature, unreacted monomer and homopolymer are fallen in reaction back extracting, promptly get the grafts that contains 4-vinylpridine (4VP).

Step 2: with embodiment 1～6

The antibacterial experiment of embodiment 1～embodiment 14 is basic identical in the table 3, promptly earlier anti-biotic material is cut into the disc that diameter is 3.3cm, is placed on the bracing frame again, and with the suspension medium of sterile purified water as bacterium, the concentration of E.coli is controlled at 10 ⁶Cells/ml adopts 1 layer of anti-biotic material, and filtering velocity is 7.5ml/min, collects 20ml filtrate, detects bacterial concentration in the effluent liquid, calculates the degerming rate.

The calculation formula of degerming rate is as follows:

Analyze the The anti-bacterial result of the foregoing description and can find following certain law:

1, for being the prepared anti-biotic material of matrix with identical PP non-woven fabrics, if quaternizing agent is identical, so, the pyridinium salt content of material is high more, the degerming rate is high more, shown in embodiment 1, embodiment 6, embodiment 7, embodiment 8, embodiment 11 and embodiment 12.

2, the existence of suitable degree of crosslinking can form certain porosity in the pyridinium salt group of anti-biotic material, though the degerming rate descends to some extent, its inhibition to water reduces greatly when filtering, shown in embodiment 1 and embodiment 3.

3, grafts and the reaction of different quaternizing agent can obtain containing the anti-biotic material of different pyridinium salt structures, and they all have and have antibiotic resistance performance, shown in embodiment 1, embodiment 2 and embodiment 5.

4, different PP non-woven fabrics matrix adopts identical prescription and processing condition, and the degerming rate of resulting anti-biotic material is also different.In general, non-woven fabrics is thick more, and the pyridinium salt content of prepared anti-biotic material is high more, and thick more in addition non-woven fabrics matrix is high more to the rejection of bacterium,

So the degerming rate of prepared anti-biotic material is high more, but big more to the inhibition of water when filtering, as embodiment 1 and embodiment 4, and shown in embodiment 7 and the embodiment 10.

In order to further specify the performance of prepared anti-biotic material, also done the antibacterial experiment of PP non-woven fabrics matrix, and the variation of the degerming rate of anti-biotic material and PP non-woven fabrics when changing filtering velocity and lamination and counting.

The antibacterial tests condition of PP non-woven fabrics is same as the previously described embodiments, and the discovery specification is 33g/m ²And 40g/m ²The degerming rate of PP non-woven fabrics be respectively 72.01% and 77.25%, and the degerming rate of the above-mentioned anti-biotic material that contains the pyridinium salt group compares with the PP non-woven fabrics all greater than 92.05%, its anti-microbial property obviously improves.

Flow velocity changes, and anti-microbial property is also different.Reference examples 1 is compared with embodiment 1, and its flow velocity is increased to 33.3ml/min, and its degerming rate descends, and is 94.05%; And PP non-woven fabrics (33g/m ²) flow velocity when being increased to 33.3ml/min, its degerming rate descends significantly, only is 56.35%.

The lamination number increases, and the degerming rate increases.Reference examples 2 is compared with embodiment 7, and the lamination number is increased to 10 layers, and when collecting the 100ml effluent liquid, its degerming reaches 99.99%; And PP non-woven fabrics (33g/m ²) the lamination number be increased to 10 layers, when collecting the 100ml effluent liquid, the degerming rate only be 81.43%.So the lamination number increases, and can improve the degerming rate effectively for the anti-biotic material that contains the pyridinium salt functional group, and improve little to the anti-microbial property of PP non-woven fabrics.

Table 1

				Embodiment 1	Embodiment 2	Embodiment 3	Embodiment 4	Embodiment 5	Embodiment 6
										The solid state chemistry grafting	PP	Consumption		????100	????100	????100	????100	????100	????100
Specification (g/m 2)		????33	????33	????33	????40	????33	????33
								????4VP				????100	????30	????100	????100	????70	????140
????DVB			????5	????5	????0	????5	????5				????10
								????BPO				????1	????3	????1	????1	????3	????4
Interfacial agents		Toluene	????10	????18	????10	????10
								Chlorobenzene						????18
		Dimethylbenzene									????18
								Nonionogenic tenside		Tween-80		????1	????4	????1	????1		????4
Polyvinyl alcohol					????4
							Deionized water			????988	????975	????988	????988	????975	????974
Temperature of reaction (℃)			????85	????90	????85	????85										????85	????85
							Reaction times (hr)			????6	????6	????6	????6	????7	????5
Graft effect	Percentage of grafting (%)		????13.3	????8.6	????10.5	????15.4										????12.5	????15.1
							4VP content (mmol/g)		????0.92	????0.60	????0.90	????1.06	????0.89	????1.04
	Quaterisation	Halohydrocarbon	Kind		Cylite	Benzyl Chloride									Cylite	Cylite	Bromohexadecane	Cylite
Consumption (mmol/g)							????1.85	????1.19	????1.81	????2.11	????1.78	????2.08
			The quaterisation temperature (℃)			????75							????75	????75	????75	????70	????80
Committee's ammonium reaction times (hr)							????6	????6	????6	????6	????8	????7
			Quaternization degree (%)			????94.3							????90.5	????96.4	????95.6	????89.8	????95.2

Table 2

				Embodiment 7	Embodiment 8	Embodiment 9	Embodiment 10	Embodiment 11	Embodiment 12
										The solution chemistry grafting	PP	Consumption		????100	????100	????100	????100	????100	????100
Specification (g/m 2)		????33	????33	????33	????40	????33	????33
								Reaction solution	Toluene			????492	????402	????414	????492	????550	????440
????4VP		????90	????180	????180	????90	????35	????130
									????DVB		????12	????12	????0	????12	????5	????27
????BPO		????6	????6	????6	????6	????10	????3
									Temperature of reaction (℃)			????85	????85	????85	????85	????85	????90
Reaction times (hr)			????4	????4	????4	????4	????5	????3
									Graft effect		Percentage of grafting (%)	????4.1	????4.6	????2.8	????5.4	????3.1	????5.1
4VP content (mmol/g)	????0.26	????0.30	????0.26	????0.35	????0.23	????0.27
							Quaterisation	Halohydrocarbon			Kind	Cylite	Cylite	Cylite	Cylite	Cylite	Cylite
Consumption (mmol/g)	????0.53	????0.60	????0.52	????0.70	????0.46	????0.54
										The quaterisation temperature (℃)			????75	????75	????75	????75	????70	????80
Committee's ammonium reaction times (hr)			????6	????6	????6	????6		????8	????7
										Quaternization degree (%)			????91.2	????91.8	????92.7	????92.1	????90.6	????90.5

Table 3

	Pyridinium salt content (mmol/g)	The lamination number	Initial bacterium liquid		Flow velocity (ml/min)	Bacterial concentration in the effluent liquid (cells/ml)	Degerming rate (%)
								Concentration (cells/ml)	Consumption (ml)
			Embodiment 1	?0.76						?1	?6.65×10 6	?20	?7.5	?1.84×10 5	?97.24
Embodiment 2	?0.51	?1			?8.47×10 6	?20	?7.5	?4.57×10 5	?94.61
			Embodiment 3	?0.76						?1	?7.02×10 6	?20	?7.5	?1.43×10 5	?97.96
Embodiment 4	?0.86	?1			?5.83×10 6	?20	?7.5	?9.50×10 4	?98.37
			Embodiment 5	?0.71						?1	?5.83×10 6	?20	?7.5	?2.82×10 5	?95.17
Embodiment 6	?0.85	?1			?7.02×10 6	?20	?7.5	?1.54×10 5	?97.83
			Embodiment 7	?0.23						?1	?6.24×10 6	?20	?7.5	?4.49×10 5	?92.81
Embodiment 8	?0.26	?1			?7.63×10 6	?20	?7.5	?4.36×10 5	?94.29
			Embodiment 9	?0.23						?1	?4.76×10 6	?20	?7.5	?2.52×10 5	?94.70
Embodiment 10	?0.31	?1			?5.27×10 6	?20	?7.5	?2.55×10 5	?95.16
			Embodiment 11	?0.21						?1	?7.61×10 6	?20	?7.5	?6.04×10 5	?92.06
Embodiment 12	?0.24	?1			?6.03×10 6	?20	?7.5	?4.31×10 5	?92.85
			PP non-woven fabrics (33g/m 2)	?0						?1	?5.61×10 6	?20	?7.5	?1.52×10 6	?72.91
PP non-woven fabrics (40g/m 2)	?0	?1			?5.61×10 6	?20	?7.5	?1.28×10 6	?77.25
			PP non-woven fabrics (33g/m 2)	?0						?1	?8.15×10 6	20	?33.3	?3.56×10 6	?56.35
PP non-woven fabrics (33g/m 2)	?0	?10			?5.61×10 6	100	?7.5	?1.04×10 6	?81.43
			Reference examples 1	?0.76						?1	?8.15×10 6	?20	?33.3	?4.85×10 5	?94.05
Reference examples 2	?0.23	?10			?6.24×10 6	100	?7.5	?6.21×10 2	?99.99

Claims (2)

1, the chemical graft process of preparation antiseptic material of pyridine salt type polymer is characterized in that adopting solid state chemistry grafted method, makes the functional group with anti-microbial activity be combined in the polymer-based carbon surface by chemical bonded refractory, and its step and processing condition are as follows:

Each component is a benchmark with polypropylene (PP) non-woven fabrics weight part

Step 1: the preparation of chemical graft thing

(1) preparation of emulsion

Dibenzoyl peroxide (BPO) 0.5～5 weight part, interfacial agents 8～20 weight parts and nonionogenic tenside 1～5 weight part and deionized water are mixed with 1000 weight part emulsions, interfacial agents nail benzene, chlorobenzene or dimethylbenzene, non-ionic surface active refers to tween-80 or polyvinyl alcohol;

(2) chemical initiation grafting reaction

Be 27～60g/m with specification earlier ²Polypropylene (PP) non-woven fabrics 100 weight parts, 4-vinylpridine (4VP) 20-150 weight part, emulsion 1000 weight parts in Vinylstyrene (DVB) O～10 weight parts and the above-mentioned steps one (1) place there-necked flask simultaneously, and letting nitrogen in and deoxidizing, after reacting 5～7 hours under 80～95 ℃, unreacted monomer and homopolymer are fallen in extracting, promptly get the grafts that contains 4-vinylpridine (4VP);

Step 2: the quaterisation of grafts

At first that step 1 is the prepared grafts that contains 4-vinylpridine (4VP) the abundant swelling of capacity ethanol, the halohydrocarbon that adds excessive 100% (amount of substance with 4VP in the grafts is a benchmark) then, and letting nitrogen in and deoxidizing, reacted 6～8 hours down at 70～80 ℃, promptly get the polymkeric substance anti-biotic material that contains the pyridine salt type grafts.

2, the chemical graft process of preparation antiseptic material of pyridine salt type polymer is characterized in that adopting solution chemistry grafting method, makes the functional group with anti-microbial activity by the chemical bond combination, and its step and processing condition are as follows:

Step 1: the preparation of chemical graft thing

With 4-vinylpridine (4VP) 20～200 weight parts, toluene 400～550 weight parts, Vinylstyrene (DVB) 0～30 weight part, BPO3～12 weight parts are made into reaction solution, are 27～60g/m with specification more earlier ²Polypropylene (PP) non-woven fabrics 100 weight parts place reaction solution fully to take out behind the dipping, put into there-necked flask, fill the nitrogen deoxygenation then, and after reacting 3～5 hours under 80～95 ℃, unreacted monomer and homopolymer are fallen in extracting, promptly get the grafts that contains 4-vinylpridine (4VP);

Step 2: the quaterisation of grafts

At first that step 1 is the prepared grafts that contains 4-vinylpridine (4VP) the abundant swelling of capacity ethanol, the halohydrocarbon that adds excessive 100% (amount of substance with 4VP in the grafts is a benchmark) then, and letting nitrogen in and deoxidizing, reacted 6～8 hours down at 70～80 ℃, promptly get the polymkeric substance anti-biotic material that contains the pyridine salt type grafts.