CN104726858B - The method that titanium base material surface in situ grows polyhydroxy dendron molecule - Google Patents
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Abstract
A kind of method that titanium base material surface in situ grows polyhydroxy dendron molecule, its step is：A material surface hydroxylatings：By end group for the organic phospho acid or inorganic phosphate monoesters of hydroxyl form unimolecule Iy self-assembled layer on titanium base material surface, titanium base material B material surface halogenizing of the surface with oh group is obtained final product：A steps are obtained into titanium base material and two ends group it is the acyl halide reagent of halogen group carrying out nucleophilic substitution, obtains titanium base material C-material surface of the surface with halogen group polyhydroxylated：The titanium base material that B steps are obtained in weakly alkaline solution, carries out substitution reaction with the aminate with hydroxyl, obtains final product the polyhydroxylated titanium base material in surface；D, repeatedly B, step C 2~6 times, obtaining superficial growth has the titanium base material of polyhydroxy dendron molecule.The method simply can fix polyhydroxy dendron molecule on titanium base material surface, improve its surface biological performance, and it is further turned into has special multi-functional biomaterial.
Description
Technical field
It is more particularly to a kind of in titanium base material surface in situ growth dendron point the present invention relates to the method for material surface modifying
The method of son.
Background technology
Titanium base material due to its good mechanical property, corrosion resistance, biocompatibility and excellent processing characteristics
It is widely used in technical field of biological material.Although titanium base material is with certain biocompatibility, total shows biologically inert,
Its surface bioactive is significantly not enough, can not meet particular requirement of the biomaterial to its surface property.It is therefore desirable to take one
Fixed surface modified method improves its surface property to improve its biology performance.At present, it is modified to titanium base material surface to have thing
Two kinds of means of reason method and chemical method.Physical modification method is mainly by plasma technology, oxidation technology etc. to titanium-based material
Material surface is modified, although such method can to a certain extent improve the biocompatibility of titanium base material, what it built
Coating stability is poor, and reliability is low, and modified titanium base material can not meet the requirement of biomaterial.Chemical modification method refers to
After titanium base material surface is formed limited activity functional groups using chemical means, then large biological molecule is grafted by chemical bond
Deng bio-active group, to improve its biology performance.But, by current chemical modification method, the titanium base material for obtaining
Surface functional groups limited amount, biology performance is improved not substantially, limits its application in technical field of biological material.
Dendron molecule is synthesized by repeating reaction of propagation, the accurate molecule of highly branched and structure.Each is repeated
Circular response increases a branched layer, referred to as " generation ".Dendritic macromole has following distinguishing feature：1st, dendron molecule has
Clear and definite molecular weight and molecular dimension, compound with regular structure, molecular volume, shape and function base all can be controlled accurately on a molecular scale
System；2nd, dendron molecule is general by core, continuous outwards branch, with the increase of algebraically and branched continuation, molecule is by opening wide
Loose condition (of surface) be changed into it is outer it is tight in pine spherical three-dimensional structure, intramolecule has wide cavity, its internal cavities and many
Planting binding site can carry drug molecule, and surface has high functional group densities；3rd, dendron molecule has reaction well to live
Property and contain ability, in the molecule the heart and molecular end can import it is substantial amounts of reactivity or functional groups.The knot of these uniquenesses
Structure, makes dendron molecule be widely applied in biological and medical field, particularly technical field of biological material.
The content of the invention
It is an object of the invention to provide a kind of method that titanium base material surface in situ grows polyhydroxy dendrimer, the party
Method simply in the fixed polyhydroxy dendron molecule of titanium base material surface in situ chemistry can not only improve its surface biological
Can, and titanium base material can be made as with special multi-functional biomaterial.
Invent to realize that the technical scheme that its goal of the invention is taken is：A kind of titanium base material surface in situ grows polyhydroxy
The method of dendron molecule, its step is：
A, material surface hydroxylating：By titanium base material temperature be 10~100 DEG C, concentration be 0.5~30mmol/L end groups
It is the organic phospho acid ((OH) of hydroxyl2POCH2(CH2)nX, 1≤n≤20, X=-OH) or inorganic phosphate monoesters ((OH)2POOCH2
(CH2)nX, 1≤n≤20, X=-OH) 1~24h is soaked in solution；By the titanium base material after immersion under the conditions of 80~150 DEG C,
5~30h of heating；Repeat aforesaid operations 3~8 times, organic phospho acid or inorganic phosphate monoesters functionalization are formed on titanium base material surface
Unimolecule Iy self-assembled layer, obtaining final product superficial growth has the titanium base material of oh group；
B, material surface halogenizing：A steps are obtained into titanium base material and is put into concentration for 0.1~1.0mg/ml two ends group is
Acyl halide reagent (X (the CH of halogen group2)nCOX, X are halogen, in the anhydrous tetrahydrofuran solution of 1≤n≤20), add alkali
Property material, adjust the pH value of solution to pH=7~10,5~36h is reacted under the conditions of 0~80 DEG C, obtain surface with halogen radical
The titanium base material of group；
C, material surface are polyhydroxylated：It is 50~100mg/ml with hydroxyl that the B titanium base materials that obtain of step are put into concentration
Aminate (the HN [(CH of base2)n OH]2, in the anhydrous tetrahydrofuran solution of 2≤n≤20), the pH of solution is adjusted through alkaline matter
Value reacts 8~15h to alkalescent (pH=7~9) under the conditions of 60~80 DEG C, obtains final product the polyhydroxylated titanium base material in surface；
D, repeatedly B, step C 2~6 times, obtaining superficial growth has the titanium base material of polyhydroxy dendron molecule.
The reaction mechanism of each step of the present invention is：
In A steps, end group is that the organic phospho acid of hydroxyl or phosphonic acids (phosphoric acid) group of inorganic phosphate monoesters can be with bridgings
Mode be connected with titanium base material surface, and form the monolayer with certain density and high-sequential, and adjacent phosphonic acids (phosphorus
Acid) hydrogen bond and stronger electrostatic interaction are there is between group, therefore, it is possible to form firm chemical bond；So, just exist
Titanium base material surface construction is containing can with the hydroxyl functional groups of carboxylic acid halides reagent reacting.
In B steps, in the basic conditions, hydroxyl and the two ends group on titanium base material surface are the carboxylic acid halides of halogen group
There is nucleophilic substitution so as to form firm chemical bond in reagent.
In C steps, under weakly alkaline environment, amino in the halogen group on titanium base material surface and the aminate with hydroxyl
On hydrogen atom continue occur substitution reaction and form strong chemical bonding.
B, step C are repeated, nucleophilic substitution and halogen group and band between hydroxyl and acyl halide reagent is just repeated
There is the substitution reaction between the aminate of hydroxyl, have the titanium base material of polyhydroxy dendron molecule so as to obtain superficial growth.
Compared with prior art, the beneficial effects of the invention are as follows：
First, the inventive method can form firmization by organic phospho acid or inorganic phosphate monoesters and titanium base material first
Learn and combine, then terminal functionality (hydroxyl) and acyl halide reagent the generation nucleophilic displacement of fluorine for passing through organic phospho acid or inorganic phosphate monoesters
, then there is substitution reaction in reaction, hydroxyl and acyl halide reagent is finally repeated by halogen with the aminate rich in hydroxyl
Nucleophilic substitution and halogen and aminate substitution reaction, generate polyhydroxy dendron molecule.Whole dendron molecule is in titanium-based
The building process of material surface is completed by classical chemical reaction, between every part is connected by chemical bond, with reference to jail
Gu, it is difficult for drop-off.
2nd, all of operating procedure is simple in the present invention, without special expensive device and chemical reagent, easily realizes,
And the three-dimensional-structure to material or implantation instrument is not limited, material body performance is had no effect, be capable of achieving industrial tool
There is the fixation of the polyhydroxy dendron molecule on the various biomedical devices surfaces of complex shape structure.
3rd, dendron molecule is introduced to titanium base material surface by the inventive method, substantially increases titanium base material surface function
Group's quantity, by the control of " generation " number of the dendron molecule to growing, can obtain with excellent anticoagulation function and good
The titanium base material of biocompatibility, also for being further modified for titanium base material provides advantage；Simultaneously as three-dimensional structure
Dendron molecule there are various unique performances such as more excellent load medicine function, can make titanium base material turn into have it is special multi-functional
Biomaterial.
Further, heretofore described titanium base material is pure titanium, titanium oxide or titanium alloy.
Further, the acyl halide reagent in heretofore described B steps is chloracetyl chloride or the bromo- 2- methyl propionyl bromides of 2-.
Further, the alkaline matter in heretofore described B steps is amine, hydroxide, sodium carbonate, sodium acid carbonate or
Pyridine.
Further, the alkaline matter in heretofore described C steps is sodium acetate, sodium acid carbonate or saleratus.
Further, the aminate containing hydroxyl is diethanol amine, dipropanolamine diisopropanol in heretofore described C steps
Amine or two butanolamines.
Brief description of the drawings
Fig. 1 is the water contact angle figure of each step material of the embodiment of the present invention 1.
In figure：The histogram for marking Ti-O is the water contact angle figure of unmodified thin film of titanium oxide；Mark the Nogata of HUPA
Figure is the water contact angle figure of the thin film of titanium oxide for completing A step self assembly 11- hydroxyundecyl phosphonic acids；Mark OH histogram be
The water contact angle figure of the thin film of titanium oxide of the growth in situ polyhydroxy dendron molecule obtained by 4 B, C operations.
Fig. 2 is the scanning electron microscope (SEM) photograph of unmodified thin film of titanium oxide surface platelet adhesion reaction in the embodiment of the present invention 1.
Fig. 3 is the oxidation of the growth in situ polyhydroxy dendron molecule obtained by 4 B, C operation in the embodiment of the present invention 1
Titanium film surface platelet adhesion reaction scanning electron microscope (SEM) photograph.
Specific embodiment
Embodiment 1
A kind of method that thin film of titanium oxide surface in situ grows polyhydroxy dendron molecule, its step is：
A, material surface hydroxylating：By thin film of titanium oxide in the 11- hydroxyls 11 that temperature is 25 DEG C, concentration is 10mmol/L
12h is soaked in the anhydrous tetrahydrofuran solution of alkyl phosphonic acid；By the thin film of titanium oxide after immersion under the conditions of 120 DEG C, vacuum adds
Hot 15h；Repeat aforesaid operations 6 times, the unimolecule self assembly of 11- hydroxyundecyl phosphonic acids is obtained on thin film of titanium oxide surface
Layer, obtaining final product superficial growth has the thin film of titanium oxide of oh group；
B, material surface halogenizing：It is 0.5mg/ml chloracetyl chloride reagents that A steps obtain thin film of titanium oxide to be put into concentration
In anhydrous tetrahydrofuran solution, anhydrous triethylamine is added, adjust the pH value of solution to pH=7, reacted under the conditions of 25 DEG C
10h, obtains thin film of titanium oxide of the surface with chlorine atom group；
C, material surface are polyhydroxylated, and the thin film of titanium oxide that B steps are obtained is put into the nothing that concentration is 100mg/ml diethanol amine
In water tetrahydrofuran solution, add the pH value of manganese hydrogen sodium regulating solution to pH=7,12h is reacted in 60 DEG C, obtain final product surface polyhydroxy
The thin film of titanium oxide of base；
D, repeatedly B, step C 4 times, obtain the thin film of titanium oxide that surface is polyhydroxy dendron molecule.
Fig. 1 shows, the water contact angle figure of each step material of the present embodiment.It can be seen that not growing polyhydroxy tree
The water contact angle of the thin film of titanium oxide of prominent molecule is big, and hydrophily is poor；After completing A step self assembly 11- hydroxyundecyl phosphonic acids, by
Cause that thin film of titanium oxide surface hydrophilicity is improved in the hydrophilic radical of 11- hydroxyundecyl phosphonic acids afterbodys；With terminal hydroxy group tree
The structure of shape molecule, hydrophilic hydroxyl quantity gradually increases, therefore the growth in situ polyhydroxy obtained by 4 B, C operations
The thin film of titanium oxide surface of base dendron molecule occurs in that super hydrophilic phenomenon.
Fig. 2 shows, the scanning electron microscope (SEM) photograph of unmodified thin film of titanium oxide surface platelet adhesion reaction in the present embodiment.From figure
As can be seen that unmodified thin film of titanium oxide surface platelet adhesion reaction quantity is many and platelet activation serious and with there is blood
Platelet clustering phenomena.
Fig. 3 shows, the oxidation of the growth in situ polyhydroxy dendron molecule obtained by 4 B, C step operations in the present embodiment
The scanning electron microscope (SEM) photograph of titanium film surface platelet adhesion reaction.It can be seen that growth in situ four generations hydroxyl dendron molecular oxidation
Titanium film surface display goes out excellent anticoagulation function, and the platelet counts of material surface adhesion are few, and platelet PLA2 keeps good
Get well and do not occur obvious state of activation.
Embodiment 2
A kind of method that thin film of titanium oxide surface in situ grows polyhydroxy dendron molecule, its step is：
A, material surface hydroxylating：By thin film of titanium oxide in the 11- hydroxyls 11 that temperature is 10 DEG C, concentration is 30mmol/L
1h is soaked in the anhydrous tetrahydrofuran solution of alkyl phosphonic acid；By the thin film of titanium oxide after immersion under the conditions of 80 DEG C, 30h is heated；
Repeat aforesaid operations 3 times, the unimolecule Iy self-assembled layer of 11- hydroxyundecyl phosphonic acids is obtained on thin film of titanium oxide surface, obtain final product
Superficial growth has the thin film of titanium oxide of oh group；
B, material surface halogenizing：A steps are obtained into thin film of titanium oxide and is put into the nothing that concentration is 1mg/ml chloracetyl chloride reagents
In water tetrahydrofuran solution, sodium acid carbonate is added, adjust the pH value of solution to pH=9,5h is reacted under the conditions of 80 DEG C, obtained
Thin film of titanium oxide of the surface with chlorine atom group；
C, material surface are polyhydroxylated：It is 50mg/ml diisopropanolamine (DIPA)s that the thin film of titanium oxide that B steps are obtained is put into concentration
Anhydrous tetrahydrofuran solution in, add the pH value of saleratus regulation solution to pH=8, react 8h in 80 DEG C, obtain final product surface
Polyhydroxylated thin film of titanium oxide；
D, repeatedly B, step C 2 times, obtain surface for polyhydroxy dendron molecular oxidation titanium film.
Embodiment 3
A kind of method that pure titanium surface in situ grows polyhydroxy dendron molecule, its step is：
A, material surface hydroxylating：By pure titanium temperature be 20 DEG C, concentration be the nothing of the Alpha-hydroxy phosphate of 20mmol/L
5h is soaked in water tetrahydrofuran solution；Pure titanium after by immersion heats 25h under the conditions of 90 DEG C；Repeat aforesaid operations 4 times,
Pure titanium surface obtains the unimolecule Iy self-assembled layer of Alpha-hydroxy phosphate, and obtaining final product superficial growth has the pure titanium of oh group；
B, material surface halogenizing：The pure titanium that A steps are obtained, is put into the bromo- 2- methyl propionyl of 2- that concentration is 0.7mg/ml
In the anhydrous tetrahydrofuran solution of bromide reagent, NaOH is added, adjust the pH value of solution to pH=8, it is anti-under the conditions of 0 DEG C
36h is answered, pure titanium of the surface with bromine atoms group is obtained；
C, material surface are polyhydroxylated：The pure titanium that B steps are obtained, it is the anhydrous of 60mg/ml dipropanolamines to be put into concentration
In tetrahydrofuran solution, add the pH value of saleratus regulation solution to pH=9, in 70 DEG C, react 10h, obtain final product surface polyhydroxy
The pure titanium of base；
D, B, step C 3 times are repeated, obtain the surface pure titanium for having a polyhydroxy dendron molecule long.
Embodiment 4
A kind of method that pure titanium surface in situ grows polyhydroxy dendron molecule, its step is：
A, material surface hydroxylating：By pure titanium in the Alpha-hydroxy phosphoric acid ester waterless that temperature is 30 DEG C, concentration is 15mmol/L
10h is soaked in tetrahydrofuran solution；Pure titanium after by immersion heats 20h under the conditions of 100 DEG C；Repeat aforesaid operations 5 times,
The unimolecule Iy self-assembled layer of the Alpha-hydroxy phosphate that pure titanium surface obtains, obtaining final product superficial growth has the pure titanium of oh group；
B, material surface halogenizing：The pure titanium that A steps are obtained, is put into the bromo- 2- methyl propionyl of 2- that concentration is 0.3mg/ml
In the anhydrous tetrahydrofuran solution of bromide reagent, pyridine is added, adjust the pH value of solution to pH=10, reacted under the conditions of 30 DEG C
30h, obtains pure titanium of the surface with bromine atoms group；
C, material surface are polyhydroxylated：The pure titanium that B steps are obtained, it is anhydrous the four of the butanolamines of 80mg/ml bis- to be put into concentration
In hydrogen tetrahydrofuran solution, add the pH value of sodium acetate regulation solution to pH=8, in 70 DEG C, react 15h, obtain final product surface polyhydroxylated
Pure titanium；
D, B, step C 6 times are repeated, obtain the surface pure titanium for having a polyhydroxy dendron molecule long.
Embodiment 5
A kind of method that pure titanium surface in situ grows polyhydroxy dendron molecule, its step is：
A, material surface hydroxylating：By pure titanium in the 11- hydroxyundecyl phosphines that temperature is 40 DEG C, concentration is 5mmol/L
18h is soaked in the anhydrous tetrahydrofuran solution of acid；Pure titanium after by immersion heats 10h under the conditions of 120 DEG C；Repeat above-mentioned behaviour
Make 6 times, the unimolecule Iy self-assembled layer of 11- hydroxyundecyl phosphonic acids is obtained on pure titanium surface, obtaining final product superficial growth has hydroxyl base
The pure titanium of group；
B, material surface halogenizing：The pure titanium that A steps are obtained, it is the anhydrous of 0.4mg/ml chloracetyl chloride reagents to be put into concentration
In tetrahydrofuran solution, sodium carbonate is added, adjust the pH value of solution to pH=8,30h is reacted under the conditions of 15 DEG C, obtain table
Pure titanium of the face with chlorine atom group；
C, material surface are polyhydroxylated：The pure titanium that B steps are obtained, it is anhydrous the four of 80mg/ml dipropanolamines to be put into concentration
In hydrogen tetrahydrofuran solution, the pH value of manganese hydrogen sodium regulating solution is added to pH=9, in 65 DEG C, react 8h, obtain final product surface polyhydroxylated
Pure titanium；
D, B, step C 3 times are repeated, obtain the surface pure titanium for having a polyhydroxy dendron molecule long.
Embodiment 6
A kind of method for growing polyhydroxy dendron molecule in pure titanium surface in situ, its step is：
A, material surface hydroxylating：By pure titanium temperature be 60 DEG C, concentration is for the Alpha-hydroxy phosphate of 2mmol/L is anhydrous
24h is soaked in tetrahydrofuran solution；Pure titanium after by immersion heats 5h under the conditions of 130 DEG C；A steps operation 7 times is repeated, pure
Titanium surface obtains the unimolecule Iy self-assembled layer of Alpha-hydroxy phosphate, and obtaining final product superficial growth has the pure titanium of oh group；
B, material surface halogenizing：The pure titanium that A steps are obtained, it is the anhydrous of 0.2mg/ml chloracetyl chloride reagents to be put into concentration
In tetrahydrofuran solution, pyridine is added, adjust the pH value of solution to pH=10,25h is reacted under the conditions of 50 DEG C, obtain surface
Pure titanium with chlorine atom group；
C, material surface are polyhydroxylated：The pure titanium that B steps are obtained, it is anhydrous the four of 70mg/ml dipropanolamines to be put into concentration
In hydrogen tetrahydrofuran solution, add the pH value of saleratus regulation solution to pH=9, in 65 DEG C, react 15h, obtain final product surface polyhydroxy
The pure titanium changed；
D, B, step C 4 times are repeated, obtain the surface pure titanium for having a polyhydroxy dendron molecule long.
Embodiment 7
A kind of method of titanium alloy surface growth in situ polyhydroxy dendron molecule, its step is：
A, material surface hydroxylating：By titanium alloy in the 11- hydroxyundecyls that temperature is 80 DEG C, concentration is 1mmol/L
24h is soaked in the anhydrous tetrahydrofuran solution of phosphonic acids；By the titanium alloy after immersion under the conditions of 150 DEG C, 18h is heated；In repetition
Operation 8 times is stated, the unimolecule Iy self-assembled layer of 11- hydroxyundecyl phosphonate monoesters is obtained in titanium alloy surface, obtain final product surface life
Length has the titanium alloy of oh group；
B, material surface halogenizing：The titanium alloy that A steps are obtained, is put into the nothing that concentration is 0.1mg/ml chloracetyl chloride reagents
In water tetrahydrofuran solution, pyridine is added, adjust the pH value of solution to pH=7,36h is reacted under the conditions of 10 DEG C, obtain table
Titanium alloy of the face with chlorine atom group；
C, material surface are polyhydroxylated：The titanium alloy that B steps are obtained, is put into the nothing that concentration is 50mg/ml diisopropanolamine (DIPA)s
In water tetrahydrofuran solution, add the pH value of sodium acetate regulation solution to pH=7, in 60 DEG C, react 15h, obtain final product surface polyhydroxy
The titanium alloy of base；
D, B, step C 5 times are repeated, obtain the surface titanium alloy for having a polyhydroxy dendron molecule long.
Embodiment 8
A kind of method in titanium alloy surface growth in situ polyhydroxy dendron molecule, its step is：
A, material surface hydroxylating：By titanium alloy in the 11- hydroxyl hendecanes that temperature is 100 DEG C, concentration is 0.5mmol/L
20h is soaked in the anhydrous tetrahydrofuran solution of base phosphonic acids；By the titanium alloy after immersion under the conditions of 130 DEG C, 15h is heated；Repeat
Aforesaid operations 8 times, the unimolecule Iy self-assembled layer of 11- hydroxyundecyl phosphonic acids is obtained in titanium alloy surface, obtains final product superficial growth
There is the titanium alloy of oh group；
B, material surface halogenizing：The titanium alloy that A steps are obtained, is put into the nothing that concentration is 0.8mg/ml chloracetyl chloride reagents
In water tetrahydrofuran solution, NaOH is added, adjust the pH value of solution to pH=9,24h is reacted under the conditions of 5 DEG C, obtained
Titanium alloy of the surface with chlorine atom group；
C, material surface are polyhydroxylated：The titanium alloy that B steps are obtained, it is the anhydrous of 85mg/ml diethanol amine to be put into concentration
In tetrahydrofuran solution, the pH value of manganese hydrogen sodium regulating solution is added to pH=9, in 80 DEG C, react 12h, obtain final product surface polyhydroxy
The titanium alloy of base；
D, B, step C 6 times are repeated, obtain the surface titanium alloy for having a polyhydroxy dendron molecule long.
Claims (6)
1. a kind of method that titanium base material surface in situ grows polyhydroxy dendron molecule, its step is：
A, material surface hydroxylating：By titanium base material temperature be 10~100 DEG C, concentration be 0.5~30mmol/L end groups be hydroxyl
The organic phospho acid (OH) of base2POCH2(CH2)nX, 1≤n≤20, X=-OH, or inorganic phosphate monoesters (OH)2POOCH2(CH2)nX,1
≤ n≤20, soak 1~24h in X=-OH solution；By the titanium base material after immersion under the conditions of 80~150 DEG C, heating 5~
30h；Repeat aforesaid operations 3~8 times, the unimolecule of organic phospho acid or inorganic phosphate monoesters functionalization is formed on titanium base material surface
Iy self-assembled layer, obtaining final product superficial growth has the titanium base material of oh group；
B, material surface halogenizing：A steps are obtained into titanium base material and is put into concentration for 0.1~1.0mg/ml two ends group is halogen
The acyl halide reagent X (CH of group2)nCOX, X are halogen, in the anhydrous tetrahydrofuran solution of 1≤n≤20, add basic species
Matter, adjusts the pH value of solution to pH=7~10, and 5~36h is reacted under the conditions of 0~80 DEG C, obtains surface and carries halogen group
Titanium base material；
C, material surface are polyhydroxylated：It is 50~100mg/ml with hydroxyl that the B titanium base materials that obtain of step are put into concentration
Aminate HN [(CH2)nOH]2, the anhydrous tetrahydrofuran solution of 2≤n≤20, through the pH value of alkaline matter regulation solution to weak base
Property, pH=7~9 are reacted 8~15h under the conditions of 60~80 DEG C, obtain final product the polyhydroxylated titanium base material in surface；
D, repeatedly B, step C 2~6 times, obtaining superficial growth has the titanium base material of polyhydroxy dendron molecule.
2. the method that a kind of titanium base material surface in situ according to claim 1 grows polyhydroxy dendron molecule, its feature
It is：The titanium base material is pure titanium, titanium oxide or titanium alloy.
3. the method that a kind of titanium base material surface in situ according to claim 1 grows polyhydroxy dendron molecule, its feature
It is：Acyl halide reagent in the B steps is chloracetyl chloride or the bromo- 2- methyl propionyl bromides of 2-.
4. the method that a kind of titanium base material surface in situ according to claim 1 grows polyhydroxy dendron molecule, its feature
It is：Alkaline matter in the B steps is amine, hydroxide, sodium carbonate, sodium acid carbonate or pyridine.
5. the method that a kind of titanium base material surface in situ according to claim 1 grows polyhydroxy dendron molecule, its feature
It is：Alkaline matter in the C steps is sodium acetate, sodium acid carbonate or saleratus.
6. the method that a kind of titanium base material surface in situ according to claim 1 grows polyhydroxy dendron molecule, its feature
It is：The aminate containing hydroxyl is diethanol amine, dipropanolamine, diisopropanolamine (DIPA) or two butanolamines in the C steps.
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| JP2011050469A (en) * | 2009-08-31 | 2011-03-17 | Japan Advanced Institute Of Science & Technology Hokuriku | Surface treatment material and surface treatment method |
| CN102000359A (en) * | 2010-12-15 | 2011-04-06 | 西南交通大学 | Method for grafting 2-methacryloyloxyethyl phosphorylcholine (MPC) polymer on titanium-base material surface |
| CN103540934A (en) * | 2013-10-21 | 2014-01-29 | 河南科技大学 | Surface-modified medical titanium metal material and preparation method thereof |
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| JP2011050469A (en) * | 2009-08-31 | 2011-03-17 | Japan Advanced Institute Of Science & Technology Hokuriku | Surface treatment material and surface treatment method |
| CN102000359A (en) * | 2010-12-15 | 2011-04-06 | 西南交通大学 | Method for grafting 2-methacryloyloxyethyl phosphorylcholine (MPC) polymer on titanium-base material surface |
| CN103540934A (en) * | 2013-10-21 | 2014-01-29 | 河南科技大学 | Surface-modified medical titanium metal material and preparation method thereof |
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