CN85108692A - Polyglycol ether is at the graft copolymerization of polyurethane surface - Google Patents

Polyglycol ether is at the graft copolymerization of polyurethane surface Download PDF

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Publication number
CN85108692A
CN85108692A CN 85108692 CN85108692A CN85108692A CN 85108692 A CN85108692 A CN 85108692A CN 85108692 CN85108692 CN 85108692 CN 85108692 A CN85108692 A CN 85108692A CN 85108692 A CN85108692 A CN 85108692A
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Prior art keywords
graft copolymerization
polyglycol ether
group
polyurethane surface
end group
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CN 85108692
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Chinese (zh)
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林思聪
刘晓宁
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Nanjing University
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Nanjing University
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Abstract

Polyglycol ether is at the polyurethane surface graft copolymerization, belong to the high-molecular biologic medical material tech field, make matrix with urethane, cerium salt is made initiator, in polyurethane surface graft copolymerization, this method can be used for preparing the high-molecular biologic medical material to the polyglycol ether that end group has a Dan Shuanjian group after metallizing.

Description

Polyglycol ether is at the graft copolymerization of polyurethane surface
Polyglycol ether belongs to the high-molecular biologic medical material tech field at the graft copolymerization of polyurethane surface.
Continuous development along with polymer science, polymeric biomaterial is medically more and more being used, people have done number of research projects to the preparation of high-molecular biologic medical material, have prepared many polymer medical materials, and are applied to human body or other organism.For example: organo-silicone rubber, urethane, polymethyl acrylic acid-beta-hydroxy ethyl ester, polyvinyl chloride and polyethylene oxide etc.But these materials, have because of mechanical property can not meet the demands, what have is relatively poor because of blood adaptability, is restricted in application.In order to improve the anticoagulation function of material, people have designed various preparation methods, in the hope of obtaining having the material of better anticoagulation function, and are exactly one of them in the method that polyurethane surface carries out graft copolymerization.For example: with cerium salt Ce 4+Acrylamide triggered graft copolymerization on poly(ether-urethene), the anticoagulation function of the product after the grafting increases than its matrix poly(ether-urethene).But because this method adopts is the small molecule monomer acrylamide, grafted chain different in size, and the grafted chain structure is line style, thereby the anticoagulation function of material awaits to improve.In order further to improve the anticoagulant property of material, the polyglycol ether that the present invention has adopted end group to have the Dan Shuanjian group carries out the graft copolymerization of urethane, and this polyethers is a kind of macromonomer, and structure can be expressed as:
CH 2=CR′R″O
Figure 85108692_IMG8
CH 2CH 2O
Figure 85108692_IMG9
nR
R is C 1~C 4Alkyl; R ' is H, CH 3; R " is
Figure 85108692_IMG10
Figure 85108692_IMG11
-CH 2-; N is 10~500.
Macromonomer is the very important intermediate of a class, and it not only itself has macromolecular character, and has the reactivity of small molecule monomer simultaneously.
For the such macromonomer of weevil base polyalkylene glycol acrylate ester, common preparation method is:
Figure 85108692_IMG12
The weak point of this method is that the pyridinium salt that reaction produces is difficult for removing in aftertreatment, need consume a large amount of solvents during washing, and product yield is not high, has only about 50% usually.
(reference: (1) " polymer communication " 281(1982);
〔2〕C.A 73 26534j〕
The objective of the invention is: the polyglycol ether macromonomer that has the Dan Shuanjian group with end group carries out graft copolymerization at polyurethane surface, its grafted chain structure is the brush type, because this structure is more near the simulation of organism, so can improve the anticoagulation function of material.
Content of the present invention is:
The first step: with excessive Join MO
Figure 85108692_IMG14
CH 2CH 2O
Figure 85108692_IMG15
nIn the toluene solution of R, 1~10 hour reaction times, 0~100 ℃ of temperature of reaction.After the reaction, filter, recrystallization promptly obtains the white powder product
Figure 85108692_IMG16
M is in the about 70~80%(formula of (I) yield: Li, Na, K, metal ions such as Rb).
Second step: with the copolymerization of urethane (PU) and the first step product (I) usefulness cerium salt initiation grafting:
Figure 85108692_IMG17
Advantage of the present invention is: carry out graft copolymerization at polyurethane surface with macromonomer, its graft effect is higher than the small molecule monomer grafting.Because its grafted chain is brush type structure, and more near the simulation of organism.For example, this is similar very to anti-thrombotic substance-mucopolysaccharide just in the structure of blood vessel surface.Therefore improved the anticoagulation function of material.On the other hand, the wetting ability of polyurethane surface also obtains bigger improvement.
The inventive method can be used for preparing the polymer medical material.The various storage blood of intravital artificial organ of biological example (artificial heart, artificial liver, artificial blood vessel, kidney machine etc.) and organism outer contacting blood hold the material of ware, device (as the blood collector in the surgical operation, blood storage container and apparatus for purifying blood etc.).
Specific examples of the present invention is: the first step 6.0g monohydroxy polyglycol ether adds in the 50ml toluene, inject the naphthalene sodium reagent, 60 ℃ are reacted half an hour, add 1.1g toluene acrylate chloride, 40 ℃ were reacted 3 hours, add molten Jie of 80ml acetone back standing over night, filtration again, filtrate is separated out solid, filtration, drying.Promptly get the polyether ester product.
Second step: reaction system is led to N 2, adding distil water 15ml, polyurethane film 0.1g adds ceric ammonium nitrate, adds the first step product polyether ester 1.5g, stirring, and reaction is 8 hours under the room temperature, takes out washing, drying.

Claims (4)

1, a kind of polyurethane surface graft copolymerization belongs to the high-molecular biologic medical material tech field.Make matrix with urethane, cerium salt is made initiator, the invention is characterized in that the polyglycol ether that adopts end group to have the Dan Shuanjian group carries out graft copolymerization at polyurethane surface, and grafted chain is brush type structure.
2, graft copolymerization according to claim 1, the chemical structural formula that wherein said end group has the polyglycol ether of Dan Shuanjian group is:
CH 2=CR′R″-O CH 2CH 2O
Figure 85108692_IMG2
nR
In the formula: R ' is H, CH - 3; R " is
Figure 85108692_IMG3
-CH 2-;
R is C 1~C 4Alkyl; N is 10~500
3, graft copolymerization according to claim 1 wherein when the polyglycol ether that said end group has a Dan Shuanjian group is:
Figure 85108692_IMG4
The time, its preparation method is: use
Figure 85108692_IMG5
And MO CH 2CH 2O
Figure 85108692_IMG7
nCH 3React in toluene solution, M is Li in the formula, Na, K, metal ions such as Rb.
4, claim 1 or 2 or 3 described graft copolymerizations can be used for preparing the polymer medical material, and the various storage blood appearance ware containers or the device of artificial organ and organism outer contacting blood can also carry out surface hydrophilic modification to polyurethane material in the organism.
CN 85108692 1985-12-21 1985-12-21 Polyglycol ether is at the graft copolymerization of polyurethane surface Pending CN85108692A (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN 85108692 CN85108692A (en) 1985-12-21 1985-12-21 Polyglycol ether is at the graft copolymerization of polyurethane surface

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN 85108692 CN85108692A (en) 1985-12-21 1985-12-21 Polyglycol ether is at the graft copolymerization of polyurethane surface

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CN85108692A true CN85108692A (en) 1987-06-24

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Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101386684B (en) * 2008-10-21 2011-08-31 东南大学 Method for preparing high hydrophilic film on medical polyurethane material surface
CN105899244A (en) * 2013-11-14 2016-08-24 pfm医用钛有限公司 Polyurethane having an antithrombogenic coating
CN109294460A (en) * 2018-10-25 2019-02-01 山东大学 A kind of UV solidification Liquid optical clear adhesive of color inhibition and preparation method thereof

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101386684B (en) * 2008-10-21 2011-08-31 东南大学 Method for preparing high hydrophilic film on medical polyurethane material surface
CN105899244A (en) * 2013-11-14 2016-08-24 pfm医用钛有限公司 Polyurethane having an antithrombogenic coating
CN105899244B (en) * 2013-11-14 2019-02-19 pfm医用钛有限公司 Polyurethane with antithrombotic coating
CN109294460A (en) * 2018-10-25 2019-02-01 山东大学 A kind of UV solidification Liquid optical clear adhesive of color inhibition and preparation method thereof

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