CN110256617A - Poly- (methyl) acrylate antibacterial agent of Han quaternary alkylphosphonium salt structure and preparation method thereof and application in the plastic - Google Patents
Poly- (methyl) acrylate antibacterial agent of Han quaternary alkylphosphonium salt structure and preparation method thereof and application in the plastic Download PDFInfo
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Abstract
Application the invention discloses poly- (methyl) acrylate antibacterial agent of Han quaternary alkylphosphonium salt structure and preparation method thereof and in the plastic.Poly- (methyl) the acrylate antibacterial agent of Han quaternary alkylphosphonium salt structure prepared by the present invention, can be used as the antibacterial additives of plastics, is used to prepare antibiotic plastic., initial decomposition temperature high quaternary alkylphosphonium salt structure good containing thermal stability that the polymer antibacterial agent is characterized in, as antibacterial additives, it can either be suitable for the process of general-purpose plastics, assign general-purpose plastics excellent antibacterial, also it can be suitable for the process of the higher engineering plastics of processing temperature, assign engineering plastics excellent antibacterial.
Description
Technical field
The present invention relates to the polymer antibacterial agents that can be used for plastics, and in particular to poly- (methyl) propylene of Han quaternary alkylphosphonium salt structure
Acid esters antibacterial agent and preparation method thereof and application in the plastic.
Background technique
The life of the mankind be unable to do without plastic products, major part household electrical appliances used in people, such as TV, refrigerator, air-conditioning, laundry
Machine, water dispenser etc. have many components all to use plastics, many public objects, as phone, computor-keyboard, various electric switches,
The frequent component of the contacts such as juvenile's toy also largely uses plastics.These surface of plastic products are easy to be contaminated by bacterial, and become
The medium that disease infects generates very big threat to people's health and life.As people are increasingly heavy to health safety issues
Depending on it is desirable to assign the plastic products in life certain antibiotic property, thus a possibility that reducing germ contamination.
Plastics itself assign plastics antibiotic property and are mainly realized by the way that antibacterial agent is added without antibiotic property.Plastics
Antibacterial agent mainly has inorganic antiseptic, small organic molecule antibacterial agent and polymer antibacterial agent three classes.The antibacterial of preceding two classes antibacterial agent
Mechanism is spillover-type Antibacterial Mechanism, i.e., has the function that antibacterial by release metal ions or small organic molecule, therefore with
Time elapses, and the antimicrobial levels inside product are constantly reduced, and antibiotic property is gradually reduced until losing completely.Meanwhile antibacterial agent
Spilling may cause damages to human health.It can solve the problem of antibacterial agent overflows using polymer antibacterial agent, reason exists
There is certain physical entanglement effect in the macromolecular chain of its macromolecular chain and plastic substrate, polymer antibacterial agent will not be with the time
Passage and be detached from plastic products.
As patent CN102690493A discloses the preparation side of antibacterial ABS containing nano silver 0.001%~0.05% a kind of
Method.Because the Antibacterial mechanism of nano silver be by silver ion overflow to achieve the effect that kill bacterium, with when
Between elapse, antibacterial effect can gradually weaken even lose.Patent CN1148106A discloses a kind of antibacterial polypropylene containing imidazolines
Preparation method.Its antibacterial agent is imidazolines small organic molecule, and similarly, as time goes by, small molecule is inside product
It releases, causes antibacterial lasting effect poor.It is total that patent CN104448557A discloses a kind of organosilicon quaternary ammonium salt polymer antibacterial agent
The preparation method of mixed modification PP.However the macromolecule thermal stability containing quaternary ammonium salt structure is not usually high, although being able to satisfy adding for PP
Work process, but not can guarantee it and can apply to the higher plastics of processing temperature.
Therefore, novel heat-proof macromolecule antibacterial agent is developed, makes it that can either be suitable for the process of general-purpose plastics, assigns
General-purpose plastics excellent antibacterial is given, can also be suitable for the process of the higher engineering plastics of processing temperature, assign engineering plastic
Expect excellent antibacterial, has a very important significance.
Summary of the invention
It is an object of the invention to overflow for existing plastics antibacterial agent, caused antibacterial timeliness is short and its own is hot
The disadvantage for stablizing difference, provides poly- (methyl) of a kind of novel structure containing quaternary alkylphosphonium salt long with antibacterial timeliness, thermal stability is good
Acrylate antibacterial agent and preparation method thereof and application in the plastic.
Above-mentioned purpose of the invention be given by following scheme it is accomplished:
Poly- (methyl) the acrylate antibacterial agent of Han quaternary alkylphosphonium salt structure, shown in structural formula such as formula (I):
M is any of 2~16 numerical value in structural formula (I), and n is any of 1~200 numerical value；
X is one of Cl, Br, I in structural formula (I)；
R in structural formula (I)1For one of hydrogen, methyl；
R in structural formula (I)2It is selected from but not limited to: methyl, ethyl, propyl, butyl, octyl, phenyl.
The preparation method of poly- (methyl) the acrylate antibacterial agent of Han quaternary alkylphosphonium salt structure of the present invention includes following step
It is rapid:
Step 1: the preparation of (methyl) acrylic acid alkyl halide base ester
Halogenated alkyl alcohol, acid binding agent and solvent are added in the reactor, acryloyl chloride or first is slowly added dropwise at 0-5 DEG C
Base acryloyl chloride, time for adding are 0.5~2h, are then stirred to react 12~48 hours, are cooled to room temperature at 15~45 DEG C, are used
Column chromatography carries out purification process to reaction product and is dried under vacuum to constant weight after completely removing unreacted raw material, obtains
(methyl) acrylic acid alkyl halide base ester.
The preparation of (methyl) acrylate antibacterial monomer of step 2: Han quaternary alkylphosphonium salt structure
(methyl) acrylic acid alkyl halide base ester, three substitution phosphines, solvent and the polymerization inhibitor of step 1 preparation are added in the reactor
Agent at 80~120 DEG C, after being stirred to react 24~72 hours, is cooled to room after the complete solvent dissolution of the substance in reactor
Temperature carries out purification process to reaction product with column chromatography, after unreacted raw material is completely removed, is dried under vacuum to constant weight,
Obtain (methyl) acrylate antibacterial monomer of Han quaternary alkylphosphonium salt structure.
The preparation of poly- (methyl) the acrylate antibacterial agent of step 3: Han quaternary alkylphosphonium salt structure
(methyl) the acrylate antibacterial monomer of Han quaternary alkylphosphonium salt structure of step 2 preparation and light-initiated is added in a reservoir
Agent, after photoinitiator is dissolved completely in monomer, with 0.5~2h of uv-light polymerization.After the completion of polymerization reaction, washed with solvent
Product is washed, unreacted monomer and oligomer are removed, obtains poly- (methyl) the acrylate antibacterial agent of Han quaternary alkylphosphonium salt structure.
The molar ratio of the pure and mild acryloyl chloride of halogenated alkyl (or methacrylic chloride) is 1:0.8~1.5 in step 1.Propylene
The molar ratio of acyl chlorides (or methacrylic chloride) and acid binding agent is 1:1.0~1.5.
Acid binding agent described in step 1 is selected from but not limited to: triethylamine, tri-n-butylamine, pyridine, 4-dimethylaminopyridine,
One of N, N- diisopropylethylamine, potassium carbonate, sodium carbonate and ammonium carbonate or more than one mixture.
Solvent described in step 1 is selected from but not limited to: acetone, butanone, cyclohexanone, tetrahydrofuran, 1,4- dioxy six
One of ring, monochloro methane, methylene chloride, chloroform, carbon tetrachloride or more than one mixture.
(methyl) acrylic acid alkyl halide base ester and three replaces the molar ratio of phosphine to be 1:0.8~1.5 in step 2, polymerization inhibitor
Dosage is the 0.1%~3% of reactant gross mass.
Solvent described in step 2 is selected from but not limited to: acetone, butanone, cyclohexanone, tetrahydrofuran, 1,4- dioxy six
Ring, dimethyl sulfoxide, n,N-Dimethylformamide, n,N-dimethylacetamide, N-Methyl pyrrolidone, acetonitrile, toluene, diformazan
One of benzene or more than one mixture.
Polymerization inhibitor described in step 2 is selected from but not limited to: 4- metoxyphenol, hydroquinone, 1,4-benzoquinone, 2,5- bis-
One of tert-butyl hydroquinone.
Photoinitiator described in step 3 is selected from but not limited to: photoinitiator 184,127,1173,2959,651,819,
One of 500, the dosage of photoinitiator is the 0.5%~3% of reactant gross mass.
Solvent described in step 3 is selected from but not limited to: acetone, butanone, cyclohexanone, tetrahydrofuran, 1,4- dioxane
One of or more than one mixture.
Alkyl in halogenated alkyl alcohol is selected from ethyl, propyl, butyl, amyl, hexyl, heptyl, octyl, nonyl, decyl, ten
One alkyl, dodecyl, tridecyl, myristyl, pentadecyl, cetyl.
The chemical equation of above-mentioned steps (by taking methacrylic chloride, the bromo- 1- undecyl alcohol of 11- and triphenylphosphine as an example)
As shown in formula (II):
Another purpose of the present invention is to provide poly- (methyl) the acrylate antibacterial agent of above-mentioned Han quaternary alkylphosphonium salt structure
Application in the plastic.Novel poly- (methyl) acrylate antibacterial agent of the invention has broad-spectrum efficient antibacterial properties, is specifically moulding
When applying in material the plastics with long acting antibiotic performance can be used to prepare individually or with the cooperation of other antibacterial agents.Wherein plastic products
Kind both includes the lower general-purpose plastics of processing temperature, also includes the higher engineering plastics of processing temperature.
Compared with prior art, the invention has the following beneficial effects:
The remarkable advantage of poly- (methyl) the acrylate antibacterial agent of novel Han quaternary alkylphosphonium salt structure of the present invention is that have
High thermal decomposition temperature is applied in plastics as antibacterial additives, has both been able to satisfy the molten of the lower general-purpose plastics of processing temperature
Melt processing, be also able to satisfy the melt-processed of the higher engineering plastics of processing temperature, and assigns their excellent antibacterials and antibacterial is held
Long property.
Specific embodiment
The present invention is further described through combined with specific embodiments below, but specific embodiment does not appoint the present invention
What is limited.
The preparation of the polymethacrylates antibacterial agent (P1) of 1 structure of quaternary alkylphosphonium salt containing cetyltributylphosphonium bromide of embodiment
The system of the polymethacrylates antibacterial agent (P1) of the present embodiment structure of quaternary alkylphosphonium salt containing cetyltributylphosphonium bromide
Preparation Method includes the following steps:
Step 1: the preparation of methacrylic acid -16- bromine hexadecane ester
The bromo- 1- hexadecanol of 16-, the 5.565g (0.055mol) of 16.067g (0.050mol) are added in single-necked flask
5.749g (0.055mol) methacrylic chloride is slowly added dropwise at 2 DEG C in triethylamine and 60ml tetrahydrofuran, and time for adding is
0.5h is then stirred to react 24 hours at 30 DEG C, is cooled to room temperature, and carries out purification process to reaction product with column chromatography,
After unreacted raw material is completely removed, it is dried under vacuum to constant weight, obtains methacrylic acid -16- bromine hexadecane ester.
Step 2: the preparation of (methacrylic acid hexadecane ester group) tributyl bromide phosphine antibacterial monomer (M1)
Methacrylic acid -16- bromine hexadecane ester, the 6.070g of 7.786g (0.02mol) are added in three-necked flask
(0.03mol) tributylphosphine and 1.4g (1wt%) hydroquinone are added the dissolution of 100ml toluene, at 100 DEG C, are stirred to react 48
After hour, it is cooled to room temperature, purification process is carried out to reaction product with column chromatography, after unreacted raw material is completely removed,
It is dried under vacuum to constant weight, obtains (methacrylic acid hexadecane ester group) tributyl bromide phosphine.
FT-IR:ν(cm-1) 2935 and 2855 (- CH2), 1721 (- C=O), 1632 (- C=C), 1113 (C-P), 726 (-
(CH2)11-、-(CH2)4-)。
1H-NMR (600MHz, DMSO-d6): δ 1.15-1.34 [39H, m] (O-CH2-CH2-(CH 2)12-CH2-CH2- P, P-
CH2-CH2-CH 2-CH 3), 140-1.63 [10H, m] (O-CH2-CH 2,-CH 2-CH2- P), 1.98 [3H, s] (- CH2=C (CH 3)),
3.58 [8H, m] (- CH 2- P), 4.08 [2H, m] (O-CH 2-CH2), 5.67 [1H, s] (CH 2=C-COO- (trans)), 6.01
[1H, s] (CH 2=C-COO- (cis)).
Step 3: the preparation of the polymethacrylates antibacterial agent (P1) of the structure of quaternary alkylphosphonium salt containing cetyltributylphosphonium bromide
5g (methacrylic acid hexadecane ester group) tributyl bromide phosphine is added in a reservoir and 0.025g (0.5wt%) light draws
Agent 1173 is sent out, after photoinitiator is dissolved completely in monomer, with uv-light polymerization 2h.After the completion of polymerization reaction, tetrahydro is used
Mixed solvent (volume ratio 1:1) washed product of furans and acetone, removes unreacted monomer and oligomer, is dried under vacuum to
Constant weight obtains P1.
FT-IR:ν(cm-1) 2938 and 2854 (- CH2), 1724 (- C=O), 1112 (C-P), 726 (- (CH2)16-、-
(CH2)4-)。
The preparation of the polymethacrylates antibacterial agent (P2) of 2 chloride containing hexyltriphenylphosphonium quaternary alkylphosphonium salt structure of embodiment
The preparation side of the polymethacrylates antibacterial agent (P2) of the present embodiment chloride containing hexyltriphenylphosphonium quaternary alkylphosphonium salt structure
Method includes the following steps:
Step 1: the preparation of the own ester of methacrylic acid -6- chlorine
Be added in single-necked flask the chloro- 1- hexanol of 6- of 6.831g (0.050mol), 7.119g (0.090mol) pyridine,
7.840g (0.075mol) methacrylic chloride is slowly added dropwise at 0 DEG C in 30ml methylene chloride and 30ml chloroform, is added dropwise
Time is 2h, is then stirred to react 12 hours, is cooled to room temperature at 45 DEG C, is carried out at purifying with column chromatography to reaction product
Reason, after unreacted raw material is completely removed, is dried under vacuum to constant weight, obtains the own ester of methacrylic acid -6- chlorine.
Step 2: the preparation of (hexyl methacrylate base) triphenyl phosphine dichloride antibacterial monomer (M2)
The own ester of methacrylic acid -6- chlorine, the 5.246g of 4.094g (0.020mol) are added in three-necked flask
100ml Isosorbide-5-Nitrae-dioxane dissolution is added in (0.020mol) triphenylphosphine and 0.280g (3wt%) 4- metoxyphenol,
It at 120 DEG C, after being stirred to react 24 hours, is cooled to room temperature, purification process is carried out to reaction product with column chromatography, by unreacted
Raw material completely remove after, be dried under vacuum to constant weight, obtain (hexyl methacrylate base) triphenyl phosphine dichloride.
FT-IR:ν(cm-1) 2935 and 2855 (- CH2), 1721 (- C=O), 1632 (- C=C), 1581,1480,1436,
1399 (phenyl ring skeletal vibrations), 1113 (C-P), 996 (P-Ph), 721 (- (CH2)6-)。
1H-NMR (600MHz, DMSO-d6): δ 1.23-1.40 [4H, m] (O-CH2-CH2-(CH 2)2-CH2-CH2- P),
[1.48-1.65 4H, m] (O-CH2-CH 2,-CH 2-CH2- P), 1.87 [3H, s] (- CH2=C (CH 3)), 3.68 [2H, m] (- CH 2-
P), 4.07 [2H, m] (O-CH 2-CH2), 5.57 [1H, s] (CH 2=C-COO- (trans)), 6.09 [1H, s] (CH 2=C-
COO- (cis)), 7.74-7.93 [15H, s] (- C6 H 5)。
Step 3: the preparation of the polymethacrylates antibacterial agent (P2) of chloride containing hexyltriphenylphosphonium quaternary alkylphosphonium salt structure
5g (hexyl methacrylate base) triphenyl phosphine dichloride and 0.025g (1wt%) photoinitiator are added in a reservoir
651, after photoinitiator is dissolved completely in monomer, with uv-light polymerization 1h.After the completion of polymerization reaction, produced with acetone washing
Object removes unreacted monomer and oligomer, is dried under vacuum to constant weight, obtains P2.
FT-IR:ν(cm-1) 2937 and 2856 (- CH2), 1721 (- C=O), 1581,1480,1436,1399 (phenyl ring bones
Frame vibration), 1113 (C-P), 996 (P-Ph), 721 (- (CH2)6-)。
The preparation of the polyacrylate antibacterial agent (P3) of the 3 quaternary alkylphosphonium salt structure of ethyl-trimethyl containing iodate of embodiment
The preparation method packet of the polyacrylate antibacterial agent (P3) of the present embodiment quaternary alkylphosphonium salt structure of ethyl-trimethyl containing iodate
Include following steps:
Step 1: the preparation of acrylic acid -2- iodo-ethyl ester
Be added in single-necked flask the ethylene iodohydrin of 8.598g (0.050mol), 3.180g (0.030mol) sodium carbonate,
3.620g (0.040mol) acryloyl chloride is slowly added dropwise at 5 DEG C in 4.146g (0.030mol) potassium carbonate and 60ml acetone, drop
It is 0.5h between added-time, is then stirred to react at 15 DEG C 48 hours, purification process is carried out to reaction product with column chromatography, it will not
After the raw material of reaction completely removes, it is dried under vacuum to constant weight, obtains acrylic acid -2- iodo-ethyl ester.
Step 2: the preparation of (ethyl acrylate base) trimethyl phosphonium iodide antibacterial monomer (M3)
Acrylic acid -2- iodo-ethyl ester, 1.217g (0.016mol) front three of 4.520 (0.02mol) are added in three-necked flask
90ml dimethyl sulfoxide and the dissolution of 10ml acetonitrile is added in base phosphine and 0.0057g (0.1wt%) 1,4-benzoquinone, and at 80 DEG C, stirring is anti-
It after answering 72 hours, is cooled to room temperature, purification process is carried out to reaction product with column chromatography, unreacted raw material is completely removed
Afterwards, it is dried under vacuum to constant weight, obtains (ethyl acrylate base) trimethyl phosphonium iodide.
FT-IR:ν(cm-1) 2935 and 2855 (- CH2), 1721 (- C=O), 1632 (- C=C), 1113 (C-P).
1H-NMR (600MHz, DMSO-d6): δ 2.46 [11H, m] (- CH 2-P-CH 3), 4.2 [2H, m] (O-CH 2-CH2),
5.83 [1H, s] (CH 2=CH-COO- (trans)), 6.12 [1H, s] (CH2=CH- COO-), 6.41 [1H, s] (CH 2=CH-
COO-(cis))。
Step 3: the preparation of the polyacrylate antibacterial agent (P3) of the quaternary alkylphosphonium salt structure of ethyl-trimethyl containing iodate
5g (propyl acrylate base) trioctylphosphine phosphonium iodide and 0.15g (3wt%) photoinitiator 184 are added in a reservoir, to
After photoinitiator is dissolved completely in monomer, with uv-light polymerization 0.5h.After the completion of polymerization reaction, washed with Isosorbide-5-Nitrae-dioxane
Product is washed, unreacted monomer and oligomer is removed, is dried under vacuum to constant weight, obtain P3.
FT-IR:ν(cm-1) 2938 and 2854 (- CH2), 1724 (- C=O), 1112 (C-P).
The anti-microbial property of (methyl) acrylate antibacterial monomer M1, M2, M3 of 4 Han quaternary alkylphosphonium salt structure of embodiment
The antibiotic property of polymer antibacterial agent is determined by the antibiotic property of monomer, since polymer antibacterial agent P1, P2, P3 are insoluble
Yu Shui, therefore, the present embodiment monomer M1, M2, M3 corresponding to three kinds of polymer antibacterial agents are to escherichia coli
(E.coli) it is tested with the anti-microbial property of staphylococcus aureus (S.aureus), parameter used by antibacterial test is most
Small Mlc (MIC) and minimum bactericidal concentration (MBC), the results are shown in Table 1.
The MIC and MBC of table 1 M1, M2, M3 to E.coli and S.aureus
Table 1 the experiment results show that (methyl) acrylate antibacterial monomer M1 of three kinds of synthesized Han quaternary alkylphosphonium salt structures,
M2, M3 all show good antibacterial property energy to staphylococcus aureus (S.aureus), and antibacterial monomer M1, M2 are uncommon to large intestine angstrom
Salmonella (E.coli) shows good antibacterial property energy, anti-microbial property ratio of the antibacterial monomer M3 to escherichia coli (E.coli)
Wanting for antibacterial monomer M1, M2 is weak, but still shows preferable anti-microbial property, illustrates the antibacterial monomer monomer of different alkyl chain structures
(M) have an impact to antibiotic property.
The thermal stability of poly- (methyl) acrylate antibacterial agent P1, P2, P3 of 5 three kinds of Han quaternary alkylphosphonium salt structures of embodiment
This implementation carries out thermogravimetric analysis to poly- (methyl) acrylate antibacterial agent P1, P2, P3 of three kinds of Han quaternary alkylphosphonium salt structures,
The results are shown in Table 2 for it.
The thermal weight loss characteristic temperature of table 2 P1, P2, P3
The result of table 2 illustrates that synthesized antibacterial agent all has higher initial decomposition temperature, is both able to satisfy processing temperature
The melt-processed of lower general-purpose plastics is also able to satisfy the melt-processed of the higher engineering plastics of processing temperature.
Embodiment 6 is prepared by the polymethacrylates antibacterial agent (P1) of the structure of quaternary alkylphosphonium salt containing cetyltributylphosphonium bromide
Antibacterial ABS plastic
Antibacterial agent P1 is first uniformly mixed by the present embodiment with ABS plastic, and the compound is then passed through double screw extruder
Melting extrusion granulation is carried out, Antibacterial ABS plastic is made.
The batten of Antibacterial ABS plastic performance test is using vulcanizing press compression molding preparation.Experimental result is as follows:
Add Antibacterial ABS plastic prepared by 6wt% antibacterial agent P1 is to the antibiotic rate of escherichia coli (E.coli)
53.96%, the antibiotic rate to staphylococcus aureus (S.aureus) is 100%；Add the anti-of 10wt% antibacterial agent P1 preparation
Bacterium ABS plastic is 99.99% to the antibiotic rate of escherichia coli (E.coli), to staphylococcus aureus (S.aureus)
Antibiotic rate is 100%, shows excellent anti-microbial property.After impregnating 30 days in 37 DEG C of distilled water, above-mentioned difference antibacterial agent contains
Two kinds of Antibacterial ABS plastics of amount to the antibiotic rate of escherichia coli (E.coli) and staphylococcus aureus (S.aureus) and
There is no statistical difference before impregnating, shows good Durability of antimicrobial effect.Two kinds of Antibacterial ABS plastics of above-mentioned difference antimicrobial levels
Tensile strength and bending strength and the ABS plastic that is not added with antibacterial agent be held essentially constant, illustrate the addition of antibacterial agent P1
Substantially will not tensile strength to ABS plastic and bending strength impact.
Embodiment 7 is prepared anti-by the polymethacrylates antibacterial agent (P2) of chloride containing hexyltriphenylphosphonium quaternary alkylphosphonium salt structure
The mechanical property and anti-microbial property of bacterium PP plastics
Antibacterial agent P2 is first uniformly mixed by the present embodiment with PP plastics, then by the compound by double screw extruder into
Row melting extrusion is granulated, and Antibacterial PP plastic is made.
The batten of Antibacterial PP plastic performance test is using vulcanizing press compression molding preparation.Experimental result is as follows:
Add Antibacterial PP plastic prepared by 10wt% antibacterial agent P2 is to the antibiotic rate of escherichia coli (E.coli)
99.99%, the antibiotic rate to staphylococcus aureus (S.aureus) is 100%, shows excellent anti-microbial property.At 37 DEG C
After impregnating 30 days in distilled water, above-mentioned Antibacterial PP plastic is to escherichia coli (E.coli) and staphylococcus aureus
(S.aureus) antibiotic rate and immersion is preceding not to have statistical difference, shows good Durability of antimicrobial effect.Above-mentioned Antibacterial PP plastic
Tensile strength and bending strength and the PP plastics that are not added with antibacterial agent be held essentially constant, illustrate the addition base of antibacterial agent P2
Originally will not tensile strength to PP plastics and bending strength impact.
The antibacterial that embodiment 8 is prepared by the polyacrylate antibacterial agent (P3) of the quaternary alkylphosphonium salt structure of ethyl-trimethyl containing iodate
The mechanical property and anti-microbial property of PA6 plastics
Antibacterial agent P3 is first uniformly mixed by the present embodiment with PA6 plastics, and the compound is then passed through double screw extruder
Melting extrusion granulation is carried out, antibacterial PA6 plastics are made.
The batten of antibacterial PA6 plastics performance test is using vulcanizing press compression molding preparation.Experimental result is as follows:
Add antibacterial PA6 plastics prepared by 10wt% antibacterial agent P3 is to the antibiotic rate of escherichia coli (E.coli)
98.24%, the antibiotic rate to staphylococcus aureus (S.aureus) is 99.99%, shows excellent anti-microbial property.37
After impregnating 30 days in DEG C distilled water, above-mentioned antibacterial PA6 plastics are to escherichia coli (E.coli) and staphylococcus aureus
(S.aureus) antibiotic rate and immersion is preceding not to have statistical difference, shows good Durability of antimicrobial effect.Above-mentioned antibacterial PA6 plastics
Tensile strength and bending strength and the PA6 plastics that are not added with antibacterial agent be held essentially constant, illustrate the addition of antibacterial agent P3
Substantially will not tensile strength to PA6 plastics and bending strength impact.
Therefore novel poly- (methyl) the acrylate antibacterial agent of Han quaternary alkylphosphonium salt structure of the present invention has conduct
Antibacterial additives, which are added in the lower general-purpose plastics of processing temperature and the higher engineering plastics of processing temperature, prepares antibiotic plastic
Potential, and on the physical mechanical property of prepared antibiotic plastic influence it is unobvious.
Claims (10)
1. poly- (methyl) the acrylate antibacterial agent of Han quaternary alkylphosphonium salt structure, which is characterized in that shown in structural formula such as formula (I):
M is any of 2~16 numerical value in structural formula (I)；
X is one of Cl, Br, I in structural formula (I)；
R in structural formula (I)1For one of hydrogen, methyl；
R in structural formula (I)2It is selected from: methyl, ethyl, propyl, butyl, octyl, phenyl.
2. poly- (methyl) the acrylate antibacterial agent of Han quaternary alkylphosphonium salt structure according to claim 1, which is characterized in that n be 1~
Any of 200 numerical value.
3. the preparation method of poly- (methyl) the acrylate antibacterial agent of Han quaternary alkylphosphonium salt structure described in claim 1, which is characterized in that
Include the following steps:
Step 1: the preparation of (methyl) acrylic acid alkyl halide base ester
Halogenated alkyl alcohol, acid binding agent and solvent are added in the reactor, at 0-5 DEG C, acryloyl chloride or methacryl is added dropwise
Chlorine, time for adding are 0.5~2h, are then stirred to react 12~48 hours, are cooled to room temperature at 15~45 DEG C, use column chromatography
Purification process is carried out to reaction product and is dried under vacuum to constant weight after completely removing unreacted raw material, obtains (methyl) propylene
Sour alkyl halide base ester；
The solvent is selected from: acetone, butanone, cyclohexanone, tetrahydrofuran, 1,4- dioxane, monochloro methane, methylene chloride,
One or more of chloroform, carbon tetrachloride；
The acid binding agent is selected from: triethylamine, tri-n-butylamine, pyridine, 4-dimethylaminopyridine, N, N- diisopropylethylamine, carbon
One or more of sour potassium, sodium carbonate and ammonium carbonate；
The preparation of (methyl) acrylate antibacterial monomer of step 2: Han quaternary alkylphosphonium salt structure
(methyl) acrylic acid alkyl halide base ester, three substitution phosphines, solvent and the polymerization inhibitor of step 1 preparation are added in the reactor, to
It after substance in reactor is completely dissolved, at 80~120 DEG C, after being stirred to react 24~72 hours, is cooled to room temperature, with column color
Spectrometry carries out purification process to reaction product and is dried under vacuum to constant weight after completely removing unreacted raw material, obtains Han quaternary phosphine
(methyl) acrylate antibacterial monomer of salt structure；
The solvent is selected from: acetone, butanone, cyclohexanone, tetrahydrofuran, Isosorbide-5-Nitrae-dioxane, dimethyl sulfoxide, N, N- diformazan
One or more of base formamide, DMAC N,N' dimethyl acetamide, N-Methyl pyrrolidone, acetonitrile, toluene, dimethylbenzene；
The polymerization inhibitor is selected from: 4- metoxyphenol, hydroquinone, 1,4-benzoquinone, one in 2,5 di tert butyl hydroquinone
Kind；
The three substitutions phosphine is selected from: tributylphosphine, triphenylphosphine or trimethyl-phosphine；
The preparation of poly- (methyl) the acrylate antibacterial agent of step 3: Han quaternary alkylphosphonium salt structure
(methyl) the acrylate antibacterial monomer and photoinitiator of the Han quaternary alkylphosphonium salt structure of step 2 preparation are added in a reservoir, to
After photoinitiator is dissolved completely in monomer, with 0.5~2h of uv-light polymerization, after the completion of polymerization reaction, production is washed with solvent
Object removes unreacted monomer and oligomer, obtains poly- (methyl) the acrylate antibacterial agent of Han quaternary alkylphosphonium salt structure；
The photoinitiator is selected from: one of photoinitiator 184,127,1173,2959,651,819,500；
The solvent is selected from: one or more of acetone, butanone, cyclohexanone, tetrahydrofuran, 1,4- dioxane.
4. the preparation method of poly- (methyl) the acrylate antibacterial agent of Han quaternary alkylphosphonium salt structure according to claim 3, feature
It is, in step 1, the halogenated alkyl alcohol is 1:0.8~1.5 with the molar ratio of the acryloyl chloride or methacrylic chloride；
The molar ratio of the acryloyl chloride or methacrylic chloride and acid binding agent is 1:1.0~1.5.
5. the preparation method of poly- (methyl) the acrylate antibacterial agent of Han quaternary alkylphosphonium salt structure according to claim 3, feature
It is, in step 2, (methyl) the acrylic acid alkyl halide base ester and three replaces the molar ratio of phosphine to be 1:0.8~1.5, polymerization inhibitor
Dosage be (methyl) acrylic acid alkyl halide base ester and three replace phosphine gross masses 0.1%~3%.
6. the preparation method of poly- (methyl) the acrylate antibacterial agent of Han quaternary alkylphosphonium salt structure according to claim 3, feature
It is, in step 3, the dosage of the photoinitiator is (methyl) acrylate antibacterial monomer quality of Han quaternary alkylphosphonium salt structure
0.5%~3%.
7. the preparation method of poly- (methyl) the acrylate antibacterial agent of Han quaternary alkylphosphonium salt structure according to claim 3, feature
It is, in step 3, the wavelength of the ultraviolet light is 280nm-400nm.
8. the preparation method of poly- (methyl) the acrylate antibacterial agent of Han quaternary alkylphosphonium salt structure according to claim 3, feature
Be, the alkyl in the halogenated alkyl alcohol be selected from ethyl, propyl, butyl, amyl, hexyl, heptyl, octyl, nonyl, decyl,
One of undecyl, dodecyl, tridecyl, myristyl, pentadecyl, cetyl.
9. poly- (methyl) the acrylate antibacterial agent of Han quaternary alkylphosphonium salt structure described in claim 1 is used as antibacterial additives in the plastic
Application.
10. in being applied described in claim 9, which is characterized in that the plastics include: polyethylene, polypropylene, polystyrene,
Polyamide, ABS plastic or PET plastic.
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