CN103937003B - The preparation method and applications of multifunction polyvinyl - Google Patents
The preparation method and applications of multifunction polyvinyl Download PDFInfo
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Abstract
A kind of preparation method of multifunction polyvinyl, including following two step: A, under the effect of initiator, make the vinyl monomer containing multiple functional group carry out graft reaction under the synergism of the second olefinic monomer with polyvinyl, prepare functional ethylene's based polyalcohol；B, co-condensation polymer is reacted with functional ethylene's based polyalcohol, the polyvinyl of preparation multifunction.The preparation method using the present invention both can be greatly improved the grafting efficiency of co-condensation polymer and polyvinyl, again can be by adjusting the structure of co-condensation polymer, make the multifunction polyvinyl of preparation not only with the matrix resin affinity that is modified, and be provided simultaneously with antistatic effect, anti-harmful microorganism effect and good biocompatibility.Can be used as antistatic agent functional master batches, anti-harmful microorganism master batch, compatilizer master batch, or the modifying agent master batch of synthetic fibers offer dyeing is provided.
Description
Technical field
The present invention relates to chemical products, particularly relate to the preparation method of a kind of multifunction polyvinyl and answer
With.
Background technology
The antistatic additive that tradition uses in the industrial production is usually with the surfactant of little molecule, and surfactant is
Molecular structure contains hydrophilic and the amphipathic compound of two kinds of groups of lipophile simultaneously, typically adds to by the way of blended
In polymer, it is enriched on the surface of polymer by the way of migration, thus plays elimination electrostatic charge, or rub in minimizing surface
Wipe, be allowed to not produce too much electrostatic charge, to reach anti-static purpose.As CN100410306C discloses a kind of by specific organic
The sulphonic acid ester squama salt that sulphonic acid ester anion and organic squama cation are formed is essence composition, and to add up to 0.1～300ppm
Concentration contain the material of alkali metal ion and/or alkaline-earth metal ions as synthesis macromolecular material antistatic additive.This
Antistatic additive can not damage the original form and aspect of synthesis macromolecular material and the transparency, and gives this synthesis macromolecular material with excellent
Different antistatic behaviour.But its durability of antistatic additive of this little molecule is poor, antistatic composition is in use easily because of water
Wash friction and come off, be therefore a kind of temporary antistatic treatment technology.And this kind of little molecule antistatic additive is thermally-stabilised
Property poor, the physical property of polymeric matrix is damaged relatively big, especially because easily run off, with contact skin after can be to people
Body causes damage.
Additionally, at antibiosis, up to now, the preparation of most of anti-biotic materials is still utilized in plastic substrate mixing
The method of inorganic antibiotic metal ion.These metal ions include silver, copper, stannum, zinc or mercury ion etc..These inorganic molecules
Antibacterial is to be enriched in material surface by migration, produces antibacterial action with antibacterial after contacting, along with the loss of antibacterial,
Its antibacterial effect is constantly decayed.Additionally, therefore heavy metal has higher toxicity to mammalian somatic cell, make in this way
There is the risk of human toxicity and environmental pollution in the anti-biotic material become, it is not accepted by people, more cannot act as with
The textile material that human body is in close contact.Such as, CN1552767A discloses and will carry out surface modification with aluminate coupling agent
Nano-TiO2Add in EVA, then carry out extruding pelletization and prepare nanometer antibacterial sterilizing plastics.It solve conventional nano TiO2
The powder body dispersing uniformity that plastics system exists is poor, and the problem such as product surface existing defects and shade deviation, but antibacterial effect
Do not highlight.CN1078227C discloses and is added directly in EVA and PE by inorganic antiseptic powder, and extruded machine is blended and makes
Antibacterial plastic concentrate.Korean Patent KR9204827B has been reported and has been joined in EVA, PU and PVC etc. by quaternary ammonium salt antibacterial, prepares anti-
The shoe pad of bacterium deodorant.
In order to solve the problems referred to above, CN1282698C discloses by solution, the melted or method of solid state reaction, by one
Planting the polyamine containing double bond to be grafted on vistanex with guanidine salt polymer, the functional polyolefin obtained can be as one
Plant antistatic or antibacterial plastic concentrate adds in polyolefin, such that it is able to realize antistatic polyolefine, antimicrobial effect.So
And, along with the reduction of methylene support number, biocompatibility improves, anti-harmful microbe function reduction；Number is supportted on the contrary along with methylene
Increase, biocompatibility decline, anti-harmful microbe function improve；With methylene support several 7 as boundary, the structure less than 7 is fitted
In as biocompatible materials, and the structure higher than 7 is suitable for use as anti-harmful microorganism material.Described in CN1282698C
Polyamine and guanidine salt polymer comprise only a kind of methylene support structure, therefore cannot hold concurrently when using as a kind of antibacterial simultaneously
Turn round and look at antibacterial effect and biocompatibility, say, that when the antibacterial effect of this polyamine with guanidine salt polymer improves, can be right
Human injury has higher risk；And in the case of safe to the human body, antibacterial effect is the best.It addition, this relatively macromole
On the double bond activity that carried the highest, carrying out to cause inefficiency when free radical grafting reacts with polyolefin substrate, therefore can
Make most polyamine can not be connected with polyolefin substrate with chemical bond with guanidine salt polymer, simply deposit in a free form
It is in polyolefin substrate, after this polyamine and guanidine salt polymer precipitate into polyolefin surfaces, has the wind of human injury
Danger.
Summary of the invention
The purpose of the present invention, it is simply that in order to solve the problems referred to above, it is provided that the preparation of a kind of multifunction polyvinyl
Method.
In order to achieve the above object, present invention employs techniques below scheme:
The preparation method of a kind of multifunction polyvinyl, comprises the following steps:
A, preparation functional ethylene's based polyalcohol:
Under the effect of initiator, make the vinyl monomer containing multiple functional group under the synergism of the second olefinic monomer
Carry out graft reaction with having the polyvinyl of structure shown in formula (1), prepare the functionalization with functional group on strand
Polyvinyl；
In formula (1), G be-COOH ,-COO (CH2) 0-10-CH3,In-CN ,-OOCCH3 ,-C1 ,-CH3 or-H
The compositions of one or more；
N is the natural number of 150-1200；
B, preparation multifunction polyvinyl:
The co-condensation polymer of structure shown in formula (2) and the functional ethylene's based polyalcohol prepared by step A are carried out chemistry anti-
Should, prepare functionalization polyvinyl；
In formula (2), A is the one in HCl, HBr, HNO3, H2CO3 or H3PO4；
H Yu i is the natural number of 0-8, but h Yu i can not be 0 simultaneously, and J is the natural number of 1-8；
R1 Yu R2 is one or more the compound compositions in following functional group, but R1 Yu R2 is not same structure；
Raw material involved in step A and weight are as follows；
Raw material involved in step B and weight are as follows；
Functional ethylene's based polyalcohol 100 parts；
Co-condensation polymer 0.1～50 parts；
Antioxidant 0～10 parts.
Graft reaction described in step A includes solution graft copolymerization reaction, melting graft reaction or solid state shear pulrerizing；
Solution graft copolymerization reaction be: the various materials in addition to initiator are joined toluene, dimethylbenzene, decahydronaphthalene, petroleum ether,
In the solvent that one or more in trichloro-benzenes and chloroform are compounding, while stirring, progressively it is warming up to 60-130 DEG C, is formed
Polyolefin content is the homogeneous solution of 5%-75%；After drum nitrogen gets rid of oxygen, divide and be gradually added initiator for 2-5 time, maintain temperature
Degree reaction 0.1-4 hour；After reaction terminates, being lowered the temperature by reaction solution, solid separates out, through filtering, obtaining functionalization second after drying
Alkenyl polymer；
Melting graft reaction is: various materials are joined after high-speed mixer is sufficiently mixed Haake, Single screw extrusion
In machine, double screw extruder, banbury, banbury mixers or mill, at 50 DEG C-350 DEG C, carry out melting graft reaction,
Response time is 1min-30min；By product cooling, pelletizing, prepare functional ethylene's based polyalcohol；
Solid state shear pulrerizing is: first by the material dissolution except vinyl polymerization beyond the region of objective existence in solvent, then with powder
Polyvinyl is sufficiently mixed uniformly, in stirred autoclave under the protection of noble gas, and warming while stirring, reaction temperature
Degree is less than the fusing point of polyvinyl, after reacting 1-8 hour, terminates reaction, prepares functional ethylene's based polyalcohol.
Preparation functionalization polyvinyl described in step B uses solution reaction or frit reaction；
Solution reaction is: functional ethylene's based polyalcohol prepared by step A and antioxidant join dimethylbenzene, toluene,
In the complex solvent of one or more in decahydronaphthalene, petroleum ether, trichloro-benzenes or chloroform, progressively it is warming up to while stirring
60-130 DEG C, form the uniform liquid of 5%-75%, after drum nitrogen gets rid of oxygen, disposably add co-condensation polymer, maintain temperature
Reacting 0.1～4 hour, after reaction terminates, lowered the temperature by reaction solution, solid separates out, through filtering, i.e. obtaining multifunction after drying
Polyvinyl；
Frit reaction is: functional ethylene's based polyalcohol, antioxidant and the co-condensation polymer step A prepared are in high mixer
Mix homogeneously, is then added to Haake, single screw extrusion machine, double screw extruder, banbury, banbury mixers or mill
In, at 50 DEG C-350 DEG C, carrying out frit reaction, the response time is 1min-30min, by product cooling, pelletizing, i.e. prepares many merits
Polyvinyl can be changed.
As shown in formula (2), the co-condensation polymer of structure is prepared as follows:
By two kinds of both-end amido NH2-R1-NH2With NH2-R2-NH2A's defined in diamine and formula (2)Guanidinesalt, is mixed with the ratio that mol ratio is 0.5-2.0 of guanidine radicals in total amido, adds in reactor, is heated to 90-
150 DEG C, react 0.5-8 hour, then be warming up to 160-250 DEG C, react 1-10 hour, obtain two kinds of polyamine and guanidinesalt
Co-condensation polymer.
Described polyvinyl is selected from ethylene, propylene, 1-butylene, 1-amylene, 1-hexene, 1-octene, 4-methyl-1-pentene
Alkene or the homopolymer of alpha-olefin or copolymer；Or ethylene-vinyl acetate copolymer, polyacrylonitrile, acrylonitrile-styrene are common
Polymers, acrylonitrile-butadiene-styrene copolymer, polystyrene, polymethyl methacrylate, polybutyl methacrylate, poly-
Methyl methacrylate is to certain herbaceous plants with big flowers esters, polymethyl acrylate, butyl polyacrylate, polymethyl acrylate, certain herbaceous plants with big flowers ester or polrvinyl chloride
Homopolymer, copolymer and their blend.
The described vinyl monomer containing multiple functional group is selected from acrylic acid, maleic anhydride, methacrylic acid, fumaric acid, clothing health
Acid, 9-undecylenic acid or glycidyl methacrylate, and acrylic acid, methacrylic acid respectively with toluene diisocynate
Ester, six methylene support diisocyanate or 4, in the unsaturated isocyanate monomer that 4 ＇ methyl diphenylene diisocyanate reactions obtain
One or more.
Described second olefinic monomer is selected from styrene, divinylbenzene, α-methyl styrene, acrylic acid methyl ester., methyl-prop
One or more in e pioic acid methyl ester, butyl acrylate or butyl methacrylate.
Described initiator is selected from 2,5-dimethyl-2, double (tert-butyl peroxy base) hexane of 5-, 2,5-dimethyl-2, the double (uncle of 5-
Butyl peroxy base) hexin-3, cumyl peroxide, benzoyl peroxide, dilauroyl peroxide, di-t-butyl peroxy isopropyl base
Benzene, peroxidating tert-butyl acetate, peroxidating (2 ethyl hexanoic acid) tert-butyl ester, 2,5-dimethyl-2,5-double (benzoyl peroxide)
Hexane, tert-butyl cumene peroxide, peroxidating 2,4-dichloro-benzoyl, chloro benzoyl peroxide, peroxidating Laurel
Tert-butyl acrylate, peroxysuccinic acid, cyclohexanone peroxide, 1, double (tert-butyl peroxide)-3 of 1-, 3,5-trimethyl-cyclohexanes, 4,
One or several in double (tert-butyl peroxide) n-butyl pentanoate of 4-, tert-butyl hydroperoxide or tert butyl peroxy benzoate
Kind.
Described antioxidant is selected from 2,6-di-t-butyl-4-ethyl-phenol, 2,6-di-tert-butyl-4-methy phenol, 2,6-bis-
The tert-butyl group-alpha, alpha-dimethyl amino-p-cresol, 2,4,6-tri-butyl-phenols, dilauryl thiodipropionate, thio-2 acid two
In (octadecyl ester), thio-2 acid two (14 ester), antioxidant 1010, antioxidant DEG C A, antioxidant B215 or antioxidant B225
One or more.
By to R1With R2Allotment, work as R1With R2ForOr
Time, obtain hydrophilic vinyl polymer, have antistatic behaviour, the colourability of acid stain and with natural fiber, timber, paper
Open, inorganic filler has good affinity；When R1 with R2 isOr it isWhen shown methylene support structure and methylene support number are more than 8, obtain hydrophobic vinyl based polyalcohol, product
There is good affinity with ink, vistanex and rubber, and there is anti-harmful microorganism performance.
The application of above-mentioned multifunction polyvinyl, by the allotment to R1 and R2, when R1 isListen the methylene support structure shown and methylene support number more than 8, R2ForShown methylene support
Structure and methylene support number are less than 8, or areTime, and formula (2)
When the content of the co-condensation polymer of shown structure is more than 5%, the multifunction polyvinyl of preparation can be as compatilizer, with mother
The form of grain is added in corresponding polymer, improves natural fiber, timber, inorganic filler polar materials and polymeric matrix
The compatibility, improve composite mechanical property.
The application of above-mentioned multifunction polyvinyl, by R1With R2Allotment, work as R1With R2ForOrTime, and the content of the co-condensation polymer of structure shown in formula (2)
During more than 5%, the multifunction polyvinyl of preparation is used as functionalization auxiliary agent, adds to corresponding poly-with the form of master batch
In compound, improve the dyeability of polymeric matrix material, lubricity, glossiness and antistatic behaviour.
The application of above-mentioned multifunction polyvinyl, by R1With R2Allotment, work as R1For
Shown methylene support structure and methylene support number are less than 8, or are Time, R2
ForShown methylene support structure and methylene support number are more than 8, or are
Time, and when the content of the co-condensation polymer of structure shown in formula (2) is more than 5%, the multifunction polyvinyl of preparation both had
There is anti-harmful microorganism performance, there is again safety, can add in corresponding polymer as anti-harmful microorganism masterbatch,
Polymeric material is made to have anti-harmful microbe performance.
The present invention, by the allotment to R1 and R2, can make the multi-functional polyvinyl shown in formula (1) advantageously
Affine in same natural material and fiber, or possess antistatic property, or make the multi-functional polyvinyl shown in formula (1)
Make natural material and fiber obtain anti-harmful microorganism function, or make polymeric material possess antistatic property.Visible, this
Bright carrying out graft reaction initially with the alkenes small molecule monomer containing functional group and polyvinyl, prepared grafting efficiency is relatively
High functional ethylene's based polyalcohol, then by co-condensation polymer and the functional ized ethylene polymer of 2 type polyamines and guanidinesalt
On functional group carry out simple chemical reaction, the grafting effect of described co-condensation polymer and polyvinyl can be greatly improved
Rate.Additionally, it is even more important that present invention employs the co-condensation polymer of 2 type polyamines and guanidinesalt, as anti-harmful micro-
When biological assistant uses, R1 and R2 can be selected by regulation, make product have concurrently anti-harmful microorganism effect and biocompatibility,
Affinity and antistatic property with natural material, it is possible to obtain a kind of existing good antibacterial effect the most safe to the human body harmless
Anti-harmful microorganism polymeric material and anti-static material.
Detailed description of the invention
Detection method:
Anti-microbial property detects: antibiotic plastic, with reference to GB15979-1995
Fungicidal properties detects: with reference to GB/T2423.16-1999
Toxicity performance detection (acute oral): with reference to GB15193-1994 and GB/T17409-1998
Surface resistivity: with reference to GB1410-89
The survey of the co-condensation polymer grafting efficiency of 2 type polyamines and guanidinesalt in the multifunction polyvinyl of preparation
Pilot production infrared spectrum, measures the relative intensity of characteristic peak before and after its extraction, according to langbobier law, can obtain grafting effect
Rate.Computing formula is:
Grafting efficiency=C2/C1*100%
Wherein, polyamine and the content (percetage by weight) of guanidine salt copolymer before and after C2 and C1 is respectively extraction.
Below by several embodiments, the invention will be further described:
Embodiment 1
With 1, the co-condensation polymer of 2 type polyamines and guanidinesalt is prepared in 6-hexamethylene diamine, 1，10-diaminodecane and phosphoguanidine copolymerization
(numbering A), and use the method for frit reaction to prepare multifunction polypropylene, then add in polypropylene matrix as masterbatch
Make polypropylene dedicated material (numbering 1#):
Take 1,6-hexamethylene diamine 58.1g, 1，10-diaminodecane 86.15g, phosphoguanidine 108.07g, join three mouthfuls of burnings of 500ml
In Ping, under nitrogen protection, stir and be warming up to 110 DEG C, reacting 1 hour, then heating to 185 DEG C and react 8 hours, finally take advantage of
Heat pours out the co-condensation polymer A obtaining 2 type polyamines with guanidinesalt.
Take polypropylene Y1600 (Kingsoft petrochemical industry, melt index 16.0g/10min) 10 kilograms, maleic anhydride grafted monomers 0.2
Kilogram, styrene 0.2 kilogram, cumyl peroxide 36 grams, whole materials are put in high-speed mixer and mix 2 minutes, go out
Material.Add mixture in the double screw extruder having been preheated with 170 DEG C, extrude with the tachyphylaxis of 50rpm.Extrusion is produced
Thing obtains functionalization polypropylene after pelletizing.
Take 4 kilograms of functionalization polypropylenes prepared by said method, 1 kilogram of 2 type prepared by said method
Polyamine and the co-condensation polymer A of guanidinesalt, the most all put in high-speed mixer and mix 2 minutes, discharging.Add mixture into
Have been preheated with in the double screw extruder of 180 DEG C, extrude with the tachyphylaxis of 80rpm.Extrusion product obtains many after pelletizing
Functional poly propylene.The polyacrylic grafting efficiency of multifunction of preparation is shown in Table 1.
Take 1 kilogram of multifunction polypropylene prepared by said method, 19 kilograms of polypropylene Y1600, all put into height
Speed mixer mixes 2 minutes, discharging.Add mixture in the double screw extruder having been preheated with 180 DEG C, with
The rotating speed extrusion of 80rpm.Extrusion product obtains 1# polypropylene dedicated material after pelletizing, and its properties is shown in Table 1.
Embodiment 2
With 1, the co-condensation polymer (numbering of 2 type polyamines and guanidinesalt is prepared in 6-hexamethylene diamine, ethylenediamine and phosphoguanidine copolymerization
B), and use the method for frit reaction to prepare multifunction polypropylene, then add in polypropylene matrix as masterbatch and make
Polypropylene dedicated material (numbering 2#):
2 type polyamines are same as in Example 1 with the synthetic method of the co-condensation polymer B of guanidinesalt, simply by 30.06g's
Ethylenediamine substitutes 1，10-diaminodecane and carries out copolyreaction, obtains the co-condensation polymer B of 2 type polyamines and guanidinesalt.It with pass through
The reaction of the functionalization polypropylene of embodiment 1 preparation is also identical with embodiment 1, the polyacrylic grafting of multifunction prepared
Efficiency is shown in Table 1.The preparation method of 2# polypropylene dedicated material is also identical with embodiment 1, and its properties is listed in table 1
In.
Embodiment 3
With 1, the co-condensation polymer (volume of 2 type polyamines and guanidinesalt is prepared in 6-hexamethylene diamine, p-phenylenediamine and phosphoguanidine copolymerization
Number C), and use the method for frit reaction to prepare multifunction polypropylene, then add in polypropylene matrix as masterbatch and make
One-tenth polypropylene dedicated material (numbering 3#):
2 type polyamines are same as in Example 1 with the synthetic method of the co-condensation polymer C of guanidinesalt, simply by 54.07g's
P-phenylenediamine substitutes 1，10-diaminodecane and carries out copolyreaction, obtains the co-condensation polymer C of 2 type polyamines and guanidinesalt.It is with logical
The reaction of the functionalization polypropylene crossing embodiment 1 preparation is also identical with embodiment 1, and prepared multifunction is polyacrylic to be connect
Branch efficiency is shown in Table 1.The preparation method of 3# polypropylene dedicated material is also identical with embodiment 1, and its properties is listed in table 1
In.
Embodiment 4
With 1, the co-condensation polymer C of 2 type polyamines and guanidinesalt is prepared in 6-hexamethylene diamine, p-phenylenediamine and phosphoguanidine copolymerization,
And use the method for frit reaction to prepare multifunction polyethylene, then add to as masterbatch and base polyethylene is made poly-second
Alkene PP Pipe Compound:
Take 2 type polyamines of 1 kilogram of embodiment 1 preparation and the co-condensation polymer C of guanidinesalt.The preparation of functional polyethylene
Method is identical with the preparation method of functionalization polypropylene in embodiment 1, and the polyethylene trade mark of use is polyethylene 2200J
(Daqing petrochemical, melt index 6.0g/10min).The co-condensation polymer C of 2 type polyamines and guanidinesalt and functional polyethylene
Reacting also identical with embodiment 1, the grafting efficiency of the multifunction polyethylene of preparation is shown in Table 1.Polyethylene special-purpose material
Preparation method also identical with embodiment 1, its properties is shown in Table 1.
Embodiment 5
With 1, the co-condensation polymer C of 2 type polyamines and guanidinesalt is prepared in 6-hexamethylene diamine, p-phenylenediamine and phosphoguanidine copolymerization,
And use the method for frit reaction to prepare multifunction ethylene-vinyl acetate copolymer (EVA), then add to as masterbatch
EVA matrix makes flame retardant EVA special material:
Take 2 type polyamines of 1 kilogram of embodiment 1 preparation and the co-condensation polymer C of guanidinesalt.The preparation side of functionalization EVA
Method is identical with the preparation method of functionalization polypropylene in embodiment 1, and the EVA trade mark of use is E182L (Samsung Dao Daer).
2 type polyamines are also identical with embodiment 1 with the reaction of functionalization EVA with the co-condensation polymer C of guanidinesalt, many merits of preparation
The grafting efficiency that can change EVA is shown in Table 1.The preparation method of flame retardant EVA special material is also identical with embodiment 1, its properties
It is shown in Table 1.
Embodiment 6
With 1, the co-condensation polymer C of 2 type polyamines and guanidinesalt is prepared in 6-hexamethylene diamine, p-phenylenediamine and phosphoguanidine copolymerization,
And use the method for frit reaction to prepare multifunction polypropylene, then add to as masterbatch and polypropylene matrix is made poly-third
Alkene PP Pipe Compound (numbering 4#):
Take 2 type polyamines of 1 kilogram of embodiment 1 preparation and the co-condensation polymer C of guanidinesalt.The preparation of functionalization polypropylene
Method is identical with the preparation method of functionalization polypropylene in embodiment 1, simply changes maleic anhydride grafted monomers into methyl
Glycidyl acrylate grafted monomers.The co-condensation polymer C of 2 type polyamines and guanidinesalt and the functionalized poly third of above-mentioned preparation
The reaction of alkene is also identical with embodiment 1, and the polyacrylic grafting efficiency of multifunction of preparation is shown in Table 1.4# polypropylene
The preparation method of PP Pipe Compound is also identical with embodiment 1, and its properties is shown in Table 1.
Embodiment 7
With 1, the co-condensation polymer C of 2 type polyamines and guanidinesalt is prepared in 6-hexamethylene diamine, p-phenylenediamine and phosphoguanidine copolymerization,
And use the method for frit reaction to prepare multifunction polypropylene, then add to as masterbatch and polypropylene matrix is made poly-third
Alkene PP Pipe Compound (numbering 5#):
Take 2 type polyamines of 1 kilogram of embodiment 1 preparation and the co-condensation polymer C of guanidinesalt.The preparation of functionalization polypropylene
Method is identical with the preparation method of functionalization polypropylene in embodiment 1, simply changes maleic anhydride grafted monomers into propylene
Acid grafted monomers.The co-condensation polymer C of 2 type polyamines and guanidinesalt and the sense of above-mentioned preparation
Changing polyacrylic reaction also identical with embodiment 1, the polyacrylic grafting efficiency of multifunction of preparation is listed in
In table 1.The preparation method of 5# polypropylene dedicated material is also identical with embodiment 1, and its properties is shown in Table 1.
Table 1
1, mildew-resistant grade: 0 grade-under magnifier without obvious mildew；1 grade-fungus growth is rare or act is unequal to existing, at sample
The area coverage on surface is less than 10%；2 grades-mycete is 10%-30% in the area coverage of sample surfaces；3 grades-mycete is at sample
The area coverage on surface is 30-60%；4 grades-mycete is more than 60% in the area coverage of sample surfaces.
2, skin irritation classification: 0-is without obvious erythema；The erythema that 1-is the slightest；The erythema that 2-is slight；3-is moderate
Erythema；The erythema that 4-is serious.
Embodiment 1-3 from table 1 is it can be seen that co-condensation polymer A, B, C of 2 type polyamines and guanidinesalt and polypropylene
Grafting efficiency all more than 97%, illustrate no matter to use the co-condensation polymer of which kind of 2 type polyamine and guanidinesalt, use this
Bright method can improve the grafting efficiency of the 2 type polyamines co-condensation polymer with guanidinesalt and acrylic resin.From enforcement
It can also be seen that owing to the methylene support structure number of ethylenediamine is less in example 1-3, the therefore cocondensation of 2 type polyamines and guanidinesalt
Polymers B shows good antistatic behaviour after being grafted on polypropylene matrix, surface resistivity only has 7.2 × 107；And due to the last of the ten Heavenly stems
Diamidogen and p-phenylenediamine contain the stronger Long carbon chain of hydrophobicity and phenyl ring, therefore 2 type polyamines and the cocondensation of guanidinesalt respectively
It is much bigger with the co-condensation polymer B of guanidinesalt that polymers A and C writes polypropylene grafted rear surface resistivity ratio 2 type polyamine.But,
Along with the minimizing of methylene support structure number, 2 type polyamines are greatly reduced with antibacterial, the anti-mold effect of the co-condensation polymer B of guanidinesalt,
Therefore the mildew-resistant grade of embodiment 2 only has I level, and bacteriostasis rate only has 75.84%, but it has good biocompatibility, skin
Skin irritant test reaches 0 grade；By comparison, co-condensation polymer A and C of 2 type polyamines and guanidinesalt all have good antibacterial,
Anti-mold effect, but owing to the decamethylene diamine in the 2 type polyamines co-condensation polymer A with guanidinesalt has longer carbon-chain structure,
Its biocompatibility is greatly reduced, and irritation test reaches 3 grades.And 2 type polyamine and the guanidines containing benzene ring structure
The co-condensation polymer C of salt not only has a preferable antibacterial and mouldproof effect, and the best biocompatibility.
Comparative example's Isosorbide-5-Nitrae, 5 it can be seen that the co-condensation polymer C of 2 type polyamines and guanidinesalt and polypropylene, polyethylene
Having higher grafting efficiency with EVA, grafting efficiency is all more than 98%.And it is antibacterial, anti-mold effect is at every kind of resin base
In body the most prominent, mildew-resistant grade reaches 0 grade, and bacteriostasis rate is all 99.99%, and biocompatibility is relatively good.
Comparative example 1,6, and 7 it can be seen that in embodiment 1 with implement in 7, single for grafting with maleic anhydride and acrylic acid
Body can improve the co-condensation polymer C of 2 type polyamines and guanidinesalt and polyacrylic grafting efficiency, does not also interfere with it and resists
Bacterium, fungicidal properties；But during with glycidyl methacrylate for grafted monomers, 2 type polyamines and the cocondensation of guanidinesalt
The grafting efficiency of polymers C is but substantially reduced, and its grafting efficiency only has 75.7%.This is possibly due to the contracting of a part of methacrylic acid
The ester group of water glyceride there occurs hydrolysis under the alkaline environment of guanidinesalt, therefore 2 type polyamines and the cocondensation of guanidinesalt
Polymers C can not be grafted on polyacrylic matrix, and causes its grafting efficiency to be greatly reduced.
Claims (11)
1. the preparation method of a multifunction polyvinyl, it is characterised in that comprise the following steps:
A, preparation functional ethylene's based polyalcohol:
Under the effect of initiator, make the vinyl monomer containing multiple functional group under the synergism of the second olefinic monomer with tool
There is the polyvinyl of structure shown in formula (1) to carry out graft reaction, prepare the functional ethylene with functional group on strand
Based polyalcohol；
In formula (1), G is-COOH ,-COO (CH2)0-10─CH3、─CN、─OOCCH3、─Cl、─CH3Or-in H
The compositions of one or more；
N is the natural number of 150-1200；
B, preparation multifunction polyvinyl:
The co-condensation polymer of structure shown in formula (2) is carried out chemical reaction with the functional ethylene's based polyalcohol prepared by step A, system
Standby functionalization polyvinyl；
In formula (2), A is HCl, HBr, HNO3、H2CO3Or H3PO4In one；
H Yu i is the natural number of 0-8, but h Yu i can not be 0 simultaneously, and J is the natural number of 1-8；
R1With R2Form for one or more in following functional group are compound, but R1With R2It it is not same structure；
The described vinyl monomer containing multiple functional group selected from acrylic acid, maleic anhydride, methacrylic acid, fumaric acid, itaconic acid, ten
One carbon enoic acid or glycidyl methacrylate, and acrylic acid, methacrylic acid respectively with toluene di-isocyanate(TDI), six sub-
One in the unsaturated isocyanate monomer that methylene diisocyanate or the reaction of 4,4' methyl diphenylene diisocyanate obtain
Or it is several.
2. the preparation method of multifunction polyvinyl as claimed in claim 1, it is characterised in that involved in step A
And raw material and weight as follows:
Raw material involved in step B and weight are as follows:
Functional ethylene's based polyalcohol 100 parts；
Co-condensation polymer 0.1～50 parts；
Antioxidant 0～10 parts.
3. the preparation method of multifunction polyvinyl as claimed in claim 1, it is characterised in that described in step A
Graft reaction include solution graft copolymerization reaction, melting graft reaction or solid state shear pulrerizing；
Solution graft copolymerization reaction is: the various materials in addition to initiator are joined toluene, dimethylbenzene, decahydronaphthalene, petroleum ether, trichlorine
In the solvent that one or more in benzene and chloroform are compounding, while stirring, progressively it is warming up to 60-130 DEG C, forms polyene
Hydrocarbon content is the homogeneous solution of 5%-75%；After drum nitrogen gets rid of oxygen, divide and be gradually added initiator for 2-5 time, maintain temperature anti-
Answer 0.1-4 hour；After reaction terminates, being lowered the temperature by reaction solution, solid separates out, through filtering, obtaining functional vinyl after drying
Polymer；
Melting graft reaction is: various materials join after high-speed mixer is sufficiently mixed Haake, single screw extrusion machine, double
In screw extruder, banbury, banbury mixers or mill, at 50 DEG C-350 DEG C, carry out melting graft reaction, reaction
Time is 1min-30min；By product cooling, pelletizing, prepare functional ethylene's based polyalcohol；
Solid state shear pulrerizing is: first by the material dissolution except vinyl polymerization beyond the region of objective existence in solvent, then with powder ethylene
Based polyalcohol is sufficiently mixed uniformly, and in stirred autoclave under the protection of noble gas, warming while stirring, reaction temperature is low
In the fusing point of polyvinyl, after reacting 1-8 hour, terminate reaction, prepare functional ethylene's based polyalcohol.
4. the preparation method of multifunction polyvinyl as claimed in claim 1, it is characterised in that described in step B
Preparation functionalization polyvinyl use solution reaction or frit reaction；
Solution reaction is: functional ethylene's based polyalcohol step A prepared and antioxidant join dimethylbenzene, toluene, decahydro
In the complex solvent of one or more in naphthalene, petroleum ether, trichloro-benzenes or chloroform, while stirring, progressively it is warming up to 60-130
DEG C, form the uniform liquid of 5%-75%, after drum nitrogen gets rid of oxygen, disposably add co-condensation polymer, maintain thermotonus 0.1
～4 hours, after reaction terminates, reaction solution to be lowered the temperature, solid separates out, through filtering, i.e. obtaining multifunction vinyl after drying
Polymer；
Frit reaction is: functional ethylene's based polyalcohol, antioxidant and the co-condensation polymer step A prepared are in high-speed mixer and mixing
Uniformly, it is then added in Haake, single screw extrusion machine, double screw extruder, banbury, banbury mixers or mill,
Carrying out frit reaction at 50 DEG C-350 DEG C, the response time is 1min-30min, by product cooling, pelletizing, i.e. prepares multi-functional
Change polyvinyl.
5. the preparation method of multifunction polyvinyl as claimed in claim 1, it is characterised in that as shown in formula (2)
The co-condensation polymer of structure is prepared as follows:
By two kinds of both-end amido NH2-R1-NH2With NH2-R2-NH2A's defined in diamine and formula (2)
Guanidinesalt, is mixed with the ratio that mol ratio is 0.5-2.0 of guanidine radicals in total amido, adds in reactor, is heated to 90-150 DEG C,
React 0.5-8 hour, then be warming up to 160-250 DEG C, react 1-10 hour, obtain two kinds of polyamine and guanidinesalt
Co-condensation polymer.
6. the preparation method of multifunction polyvinyl as claimed in claim 1, it is characterised in that described vinyl gathers
Compound is selected from ethylene, propylene, 1-butylene, 1-amylene, 1-hexene, 1-octene, 4-methyl-1-pentene homopolymer or copolymer；Or
Person's ethylene-vinyl acetate copolymer, polyacrylonitrile, acrylonitritrile-styrene resin, acrylonitrile-butadiene-styrene (ABS) copolymerization
Thing, polystyrene, polymethyl methacrylate are to ester in the last of the ten Heavenly stems, polymethyl acrylate, butyl polyacrylate, polyacrylic acid ester in the last of the ten Heavenly stems or poly-
The homopolymer of vinyl chloride, copolymer and their blend.
7. the preparation method of multifunction polyvinyl as claimed in claim 2, it is characterised in that described second alkene
Monomer selected from styrene, divinylbenzene, α-methyl styrene, acrylic acid methyl ester., methyl methacrylate, butyl acrylate or
One or more in butyl methacrylate；
Described initiator is selected from double (tert-butyl peroxy base) hexane of 2,5-dimethyl-2,5-, double (the tertiary fourth mistake of 2,5-dimethyl-2,5-
Epoxide) hexin-3, cumyl peroxide, benzoyl peroxide, dilauroyl peroxide, di-t-butyl peroxy isopropyl base benzene, mistake
Double (benzoyl peroxide) hexane of oxidation tert-butyl acetate, peroxidating (2 ethyl hexanoic acid) tert-butyl ester, 2,5-dimethyl-2,5-,
Tert-butyl cumene peroxide, peroxidating 2,4 dichloro benzene formyl, chloro benzoyl peroxide, the tertiary fourth of peroxylauric acid
Double (the tert-butyl peroxide)-3,3,5-trimethyl-cyclohexane of ester, peroxysuccinic acid, cyclohexanone peroxide, 1,1-, 4,4-are double
One or more in (tert-butyl peroxide) n-butyl pentanoate, tert-butyl hydroperoxide or tert butyl peroxy benzoate；
Described antioxidant is selected from 2,6-di-t-butyl-4-ethyl-phenol, 2,6-di-tert-butyl-4-methy phenol, 2, the tertiary fourth of 6-bis-
Base-alpha, alpha-dimethyl amino-p-cresol, 2,4,6-tri-butyl-phenols, dilauryl thiodipropionate, thio-2 acid two (18
Ester), thio-2 acid two (14 ester), antioxidant 1010, antioxidant CA, one in antioxidant B215 or antioxidant B225 or
Several.
8. the preparation method of multifunction polyvinyl as claimed in claim 1, it is characterised in that by R1With R2
Allotment, work as R1With R2ForTime, obtain hydrophilic ethylene base
Polymer, has antistatic behaviour, the colourability of acid stain and has good parent with natural fiber, timber, paper, inorganic filler
And property；Work as R1With R2ForOr it isShown methylene support structure and
When methylene support number is more than 8, obtaining hydrophobic vinyl based polyalcohol, product has good with ink, vistanex and rubber
Affinity, and there is anti-harmful microorganism performance.
9. the application of the multifunction polyvinyl that prepared by method described in claim 1, it is characterised in that by R1With
R2Allotment, work as R1ForShown methylene support structure and methylene support number are more than 8, R2For
Shown methylene support structure and methylene support number are less than 8, or are
Time, and when the content of the co-condensation polymer of structure shown in formula (2) is more than 5%, the multifunction polyvinyl of preparation can be made
For compatilizer, add in corresponding polymer with the form of master batch, improve natural fiber, timber, inorganic filler isopolarity material
Material and the compatibility of polymeric matrix, improve the mechanical property of composite.
10. the application of the multifunction polyvinyl that prepared by method described in claim 1, it is characterised in that by R1With
R2Allotment, work as R1With R2ForTime, and shown in formula (2)
When the content of the co-condensation polymer of structure is more than 5%, the multifunction polyvinyl of preparation is used as functionalization auxiliary agent, with mother
The form of grain is added in corresponding polymer, improves the dyeability of polymeric matrix material, lubricity, glossiness and antistatic
Property.
The application of multifunction polyvinyl prepared by method described in 11. claim 1, it is characterised in that by R1With
R2Allotment, work as R1ForShown methylene support structure and methylene support number are less than 8, or areTime, R2ForShown methylene support knot
Structure and methylene support number are more than 8, or areTime, and the copolycondensation of structure shown in formula (2)
When the content of thing is more than 5%, the multifunction polyvinyl of preparation had both had anti-harmful microorganism performance, had had again safety
Property, can add in corresponding polymer as anti-harmful microorganism masterbatch, make polymeric material have anti-harmful microorganism
Performance.
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| CN106800652B (en) * | 2017-01-26 | 2019-08-06 | 上海富元塑胶科技有限公司 | Guanidine oligomer and preparation method thereof and the application being bonded on polymers for general use strand |
| CN110408278B (en) * | 2019-09-05 | 2021-06-04 | 上海富元塑胶科技有限公司 | Intrinsic functional coating and preparation and application thereof |
| CN112745456B (en) * | 2019-10-30 | 2022-07-12 | 中国石油化工股份有限公司 | Flame-retardant antibacterial agent, preparation method and application thereof, and flame-retardant antibacterial thermoplastic resin composition |
| CN112521600A (en) * | 2020-11-13 | 2021-03-19 | 上海明涌新材料有限公司 | Guanidine salt polymer and preparation method and application thereof |
| CN113234298A (en) * | 2021-06-10 | 2021-08-10 | 江苏宝源高新电工有限公司 | High-performance LDPE ionic polymer and preparation method thereof |
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| CN101210061A (en) * | 2006-12-27 | 2008-07-02 | 华东理工大学 | Functional olefin copolymers and its preparing process and application |
| CN101812160A (en) * | 2009-02-23 | 2010-08-25 | 上海富元塑胶科技有限公司 | Polyolefin functional master batch, preparation method thereof and use thereof |
| CN102757565A (en) * | 2012-07-31 | 2012-10-31 | 上海富元塑胶科技有限公司 | Preparation method of long chain branched polyethylene |
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| GB824168A (en) * | 1954-10-20 | 1959-11-25 | Chemstrand Corp | A process for imparting antistatic and other properties to fibres or other articles containing acrylonitrile polymers |
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