CN1687202A - Method for preparing light stable composite inorganic/organic corpuscles containing hindered amine - Google Patents
Method for preparing light stable composite inorganic/organic corpuscles containing hindered amine Download PDFInfo
- Publication number
- CN1687202A CN1687202A CN 200510018439 CN200510018439A CN1687202A CN 1687202 A CN1687202 A CN 1687202A CN 200510018439 CN200510018439 CN 200510018439 CN 200510018439 A CN200510018439 A CN 200510018439A CN 1687202 A CN1687202 A CN 1687202A
- Authority
- CN
- China
- Prior art keywords
- hindered amine
- type
- compound
- reaction
- epoxy
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
Landscapes
- Compositions Of Macromolecular Compounds (AREA)
- Polyurethanes Or Polyureas (AREA)
Abstract
The present invention relates to a preparation method of photostabilizer containing hindered amine, in particular, it relates to a preparation method of photostability organic/inorganic compound particle containing hindered amine. Said method includes the following steps: 1). using amino silane coupling agent to treat hydrophilic silicon dioxide whose average grain size is the range of 0.01-30 micrometers; 2), using piperidol type hindered amine compound, and making it be reacted with one of three compounds of diisocyanate compound, epoxy resin and their mixture to obtain product 2. and 3). making the product 2 and product 1 be reacted so as to obtain the invented product.
Description
Technical field
The present invention relates to a kind of preparation method of hindered amine as light stabilizer, be specifically related to a kind of light stability that contains hindered amine (Hindered Amine) structure inorganic/manufacture method of organic composite microparticle, this micropartical can be used as the photostabilizer of macromolecular materials such as urethane, Resins, epoxy.
Background technology
In recent years, because oil price is surging, the Research on Weatherability of organic polymer material has become one of the most popular research topic.Hindered amine as light stabilizer HALS (Hindered Amine Light Stabilizer) is a kind of photostabilizer of developing the end of the seventies, because HALS has the weather resistance that makes the macromolecular material uniqueness, so still become one of the most general photostabilizer of outdoor macromolecular material so far.The representation compound of external HALS as the formula (3), trade name is Sanol LS-770.
Bis(2，2，6，6-tetramethyl-4-piperidinyl)sebacate
(Sanol?LS-770)
(3)
Though Sanol LS-770 class lower molecular weight HALS is widely as the photostabilizer of outdoor macromolecular material, but owing to lower molecular weight HALS compound easily from material internal to reasons such as its surface transport, volatilization and decomposition, reduced the outdoor application life-span of macromolecular material, made its weathering resistance variation.Therefore, the volatility resistance that macromoleization caused by HALS just seems especially important, as having put down in writing the various means and the method for HALS macromoleization in the patents such as the Japanese Patent No. 29552426 flat 06-206866, of, Te Open Te Open 2001-49151 and United States Patent (USP) 5856491.
But all effort of these HALS macromoleization nearly all are the methods that adopts organic substance synthetic macromolecule HALS, though have with the macromolecular material intermiscibility well, not volatile characteristics exist the synthesis technique complexity, the shortcoming that manufacturing cost is too high.Simultaneously because the HALS organic macromoleculeization makes HALS be hindered from the migration of material internal to its surface, and the addition in macromolecular material will increase, because the light stability of material and weathering resistance mainly are by the superficiality the subject of knowledge and the object of knowledge decision of material.
Because generally the amount of the HALS that adds in macromolecular material is bigger, account for the 0.1-1wt% of polymer materials usually, along with the rapid growth of outdoor macromolecular material, a large amount of uses of HALS compound can make the cost of macromolecule product increase greatly.
Summary of the invention
The object of the present invention is to provide a kind of light stability that contains hindered amine inorganic/preparation method of organic composite microparticle, be the high efficiency that can reduce the addition of HALS compound in the material when making HALS compound macromoleization again and can keep its HALS.
In order to address the above problem, technical scheme of the present invention is: the light stability that contains hindered amine is inorganic/and the preparation method of organic composite microparticle, it is characterized in that it comprises the steps: 1). use the represented wetting ability silicon-dioxide of amino one type of silane coupling agent treatment median size in the scope of 0.01-30 μ m of general expression (1);
H
2N-(R
1-NH)
n-R
2-Si-(R
3)(R
4)(R
5)?????(1)
In the formula (1): R
1, R
2Be respectively the alkyl that the charcoal atomicity is 1-4, R
3, R
4, R
5Be respectively hydrogen atom, the charcoal atomicity is alkyl, the siloxy of 1-3, n is the integer of 0-5; The consumption of amino one type of silane coupling agent is the 3-40wt% of wetting ability silicon-dioxide, and amino one type of silane coupling agent is made the amino one type of silane coupling agent aqueous solution that concentration is 0.5-3wt%; The reaction times of amino one type of silane coupling agent and wetting ability silicon-dioxide is 5-100 minute, filters the solids dry 15-17h under 35-65 ℃ vacuum that obtains, and gets product 1;
2). represented piperidinol type hindered amine compound of general expression (2) and one of following three kinds reaction then, a. diisocyanate compound, b. Resins, epoxy, c. diisocyanate compound and Resins, epoxy, product 2;
Y is the alkyl of charcoal atomicity 1-18 in the formula (2), and the addition of piperidinol type hindered amine compound is the 1-30wt% of wetting ability silicon-dioxide; If when adopting the reaction of piperidinol type hindered amine compound and diisocyanate compound, must in non-proton organic solvent, carry out, at 40-70 ℃ temperature range internal reaction 2-3h, the equivalence ratio of its piperidinol type hindered amine compound and diisocyanate compound is 1: 1.5-3.5; If when adopting the reaction of piperidinol type hindered amine compound and Resins, epoxy, reaction must be carried out in non-proton organic solvent, at 70-90 ℃ temperature range internal reaction 2-3h, the equivalence ratio of piperidinol type hindered amine compound and Resins, epoxy is 1: 1.5-3.5; If when adopting the mixture reaction of piperidinol type hindered amine compound and diisocyanate compound and Resins, epoxy, piperidinol type hindered amine compound and diisocyanate compound are 1 with the equivalence ratio of mixing of Resins, epoxy: 1.5-3.5, wherein, the equivalence ratio of diisocyanate compound and Resins, epoxy is arbitrarily.
3). with product 2 and product 1 reaction; Step 2) in if when adopting piperidinol type hindered amine compound and diisocyanate compound, temperature of reaction is at 90-110 ℃ of scope internal reaction 2-10h, component distillation is removed non-proton organic solvent and water, product (light stability that contains hindered amine inorganic/organic composite microparticle); Step 2) if when adopting piperidinol type hindered amine compound and Resins, epoxy, at 70-90 ℃ temperature range internal reaction 2-3h, component distillation is removed non-proton organic solvent and water in, product; If when adopting the reaction of piperidinol type hindered amine compound and diisocyanate compound and Resins, epoxy, at 70-90 ℃ temperature range internal reaction 2-3h, component distillation is removed non-proton organic solvent and water, get product.
Described step 1) or step 2) in can add organic silicone oil or modification organic silicon oil, kinetic viscosity is generally at 1-10 ten thousand mm
2In/s the scope, addition is the 0.5-5wt% of wetting ability silicon-dioxide.
Described step 1) or step 2) in can add the fluorinated interfacial agent, addition is the 0.1-2wt% of wetting ability silicon-dioxide.
Described non-proton organic solvent is toluene or dimethylbenzene.
Described diisocyanate compound is aliphatic diisocyanate and the aromatic diisocyanate of carbonatoms 4-20.
Described diisocyanate compound is a hexamethylene diisocyanate, 2,4-or 2,6-tolylene diisocyanate or naphthalene diisocyanate.
Described wetting ability silicon-dioxide median size is 0.01-20 μ m.
The reaction times of described amino one type of silane coupling agent and wetting ability silicon-dioxide is 20-60 minute.
The consumption of described amino one type of silane coupling agent is the 5-20wt% of wetting ability silicon-dioxide.
Described Resins, epoxy is glycidyl ether based epoxy resin, glycidyl ester based epoxy resin class, Racemic glycidol amine epoxy resin, aliphatic epoxy compound or alicyclic epoxide compound.
The wetting ability silicon-dioxide that the present invention uses, its median size preferably use the silicon-dioxide in the 0.01-20 mu m range in the scope of 0.01-30 μ m.Particle diameter is during greater than 30 μ m, and the micropartical that obtains is difficult for and the macromolecular material uniform mixing, and particle diameter is during less than 0.01 μ m, and raw material is difficult for obtaining and can causing operational difficulty.
The present invention does not have special requirement to amino one type of silane coupling agent kind, purity, rerum natura etc., general amino one type of silane coupling agent all can use, as aminoethyl aminopropyl trimethoxysilane, γ-second diamino propyl-triethoxysilicane, γ-An Bingjisanyiyangjiguiwan, own diamino Union carbide A-162, γ-divinyl triammonium base propyl-triethoxysilicane etc.
Among the present invention, the reaction of wetting ability silicon-dioxide and amino one type of silane coupling agent is at room temperature to carry out, general prewired amino one type of silane coupling agent aqueous solution that concentration is 0.5-3wt% and then the wetting ability silicon-dioxide that adds made.Amino one type of silane coupling agent has good water-soluble, can be made into the aqueous solution of quite stable.The reaction times of amino one type of silane coupling agent and wetting ability silicon-dioxide is 5-100 minute, and optimum reacting time is 20-60 minute.
Among the present invention, through the silicon-dioxide after the amino one type of silane coupling agent treatment, the amino on its surface can react with the piperidinol type hindered amine compound shown in the general expression (2) and the reaction product of diisocyanate cpd or epoxy resin compound, generate the hydrophobicity coating layer or the hydrophobic-hydrophilic amphiphilic matchmaker coating layer of long charcoal chain at silica sphere, then contain piperidines alcohols residue at the end of long charcoal chain.
Among the present invention, the common consumption of amino one type of silane coupling agent is the 3-40wt% of wetting ability silicon-dioxide, and optimum amount is 5-20wt%.When amino one type of silane coupling agent consumption when the 3wt% of wetting ability silicon-dioxide is following, reactivity variation with silicon-dioxide, reactivity with the silicon-dioxide after the amino one type of silane coupling agent treatment and diisocyanate resin or Resins, epoxy compounds is also lower, and the content of piperidines alcohols residue is also very low.When amino one type of silane coupling agent consumption when the 40wt% of wetting ability silicon-dioxide is above, the dry difficulty of disperseing to bring is given in the easy aggegation of the composite microparticle that is generated.
Among the present invention, the reaction of amino one type of silane coupling agent and wetting ability silicon-dioxide also can be used spray method except aqua-solution method.Spray method is earlier the wetting ability silicon-dioxide powdery to be dropped in decollator or the mixing machine, contains the aqueous solution of amino one type of silane coupling agent or the mixing solutions of water and organic solvent while stir to the silicon-dioxide powdery sprinkling.
The diisocyanate compound that the present invention uses has aliphatic diisocyanate and the aromatic diisocyanate of carbonatoms as 4-20, the preferably aliphatic diisocyanate of charcoal atomicity 6-14 or aromatic diisocyanate, be generally hexamethylene diisocyanate, 2,4-or 2, the 6-tolylene diisocyanate, naphthalene diisocyanate etc.
The reaction ratio of piperidinol type hindered amine compound that general expression (2) is represented and diisocyanate compound is 1: 1.5-3.5 (equivalence ratio).Consumption as the piperidinol type hindered amine compound just increases two end productses of vulcabond above this scope easily, and the result makes its forfeiture reactive behavior, can not continue and the silicon dioxde reaction of crossing through amino one type of silane coupling agent treatment.This reaction must be carried out in non-proton organic solvent, as toluene, and dimethylbenzene etc.Generally at 40-70 ℃ temperature range internal reaction 2-3h, the content of available gas chromatography determination piperidinol type hindered amine compound is confirmed reaction end thus.
For two end productses that make vulcabond reduce to minimum, generally can in containing the toluene solution of vulcabond, drip the toluene solution that contains the piperidinol type hindered amine compound lentamente.Reaction need not be removed toluene after ending from resultant, can directly add silicon-dioxide oar material (undried) or the SiO 2 powder (dried) crossed through amino one type of silane coupling agent treatment and proceed reaction.Temperature of reaction is 40-70 ℃ scope, and the reaction times is 2-3h, can remove toluene and water by component distillation in 90-110 ℃ of scope at last.
The present invention does not have special requirement to the Resins, epoxy that uses, as glycidyl ether based epoxy resin, glycidyl ester based epoxy resin class, Racemic glycidol amine epoxy resin, aliphatic epoxy compound and alicyclic epoxide compound.Can be bifunctional Resins, epoxy, also can be the polyfunctional group resin, can be liquid-state epoxy resin, also can be solid epoxy resin.
The reaction ratio of piperidinol type hindered amine compound that general expression (2) is represented and Resins, epoxy is 1: 1.5-3.5 (equivalence ratio).Consumption as the piperidinol type hindered amine compound just increases two end productses of epoxy compounds above this scope easily, is unfavorable for continuing and the silicon dioxde reaction of crossing through amino one type of silane coupling agent treatment.This reaction must be carried out in non-proton organic solvent, as toluene, and organic solvents such as dimethylbenzene.Generally,, confirm reaction end thus with the content of gas chromatography determination piperidinol type hindered amine compound at 70-90 ℃ temperature range internal reaction 2-3h.After reaction ends, the Resins, epoxy product need not separate with organic solvent, can directly add the dried silica of crossing through amino one type of silane coupling agent treatment, continuation boils off inorganic/organic composite microparticle that organic solvent promptly obtains containing the hindered amine structure at last at 70-90 ℃ temperature range internal reaction 2-3h.
In above-mentioned reaction, can add an amount of diisocyanate compound and the hydroxyl reaction of Resins, epoxy, can regulate the hydrophobic hydrophilic balance of composite microparticle, can form inierpeneirating network structure in silica particle surface simultaneously.
According to method of the present invention, in the manufacturing processed of the inorganic/organic composite microparticle that contains the hindered amine structure, can add organic silicone oil or fluorinated interfacial agent, what obtain is dispersed good composite microparticle.Can be at piperidinol type hindered amine compound and diisocyanate resin or/and add during the Resins, epoxy reaction, also can with the silicon dioxde reaction handled the time, add.
Inorganic/the organic composite microparticle that contains the hindered amine structure of the present invention, its surface coated organic silicone oil or fluorinated interfacial agent can be avoided interparticle bonding, make its micropartical have the function of " particlized " and " oil application ".
There is no particular limitation to the kind of the organic silicone oil that uses in the present invention, but preferably select the non-reactive organic silicone oil of straight chain shape siloxane structure for use, such as non-reacted dimethyl silicone oil, methyl phenyl silicone oil, the alkyls modified silicon oil, polyethers modified silicon oil and fatty acid modified silicone oil, the kinetic viscosity of organic silicone oil are generally at 1-10 ten thousand mm
2In/S the scope, and the optimum range of addition is the 0.5-5wt% of silicon-dioxide.When being lower than 0.5wt%, prevent the aggegation weak effect, when being higher than 5wt%, prevent that the aggegation effect from not having significantly raising and having increased raw materials cost.
General fluorine-containing interfacial agent can make hydrophobicity inorganic/surface energy of organic composite microparticle reduces significantly, even also can demonstrate fabulous additive effect under extremely low concentration.The fluorine-containing interfacial agent that the present invention uses has with the R of perfluor charcoal chain as hydrophobic group
fThe X structure, general R
fCarbonatoms be more than 8, X is basic metal class (Li, Na, sulfonate groups K) or carboxylate groups.
The addition of fluorinated interfacial agent is generally in the 0.1-2wt% scope, and it prevents the aggegation DeGrain addition beyond this scope, and manufacturing cost is increased.
In sum, the present invention makes it have " particlized " and " oil application " when making the HALS macromoleization as can be known, makes it to be easy to be gathered in the unique Photostabilised effect of surface performance of organic materials.
The light stability that contains hindered amine structure is inorganic/and organic composite microparticle can mix with macromolecular materials such as urethane, Resins, epoxy widely mutually; and make it to be gathered in the surface of material by its " particlized " and " oil application ", playing the usage quantity that can reduce HALS to material in the Photostabilised provide protection.
Embodiment
Below the present invention is illustrated in more detail, but protection scope of the present invention is not subjected to the qualification of embodiment.Raw material:
1. amino one type of silane coupling agent SH-6020
NH
2CH
2CH
2NHCH
2CH
2CH
2Si(OMe)
3
Toray Dow Corning Silicone produces
2. wetting ability silicon-dioxide ZEOSIL 200
J.M.Huber Corporation produces
3.1,2,2,6,6-pentamethyl--4-piperidines alcohol (PEMP)
EUTEC?Chemical?Co.
4.2,4 and 2, the mixture of 6-tolylene diisocyanate (TDI)
Asahi Chemical Industry's (strain) produces
5. methylene diphenyl diisocyanate (MDI)
Asahi Chemical Industry's (strain) produces
6. bisphenol A type epoxy resin CYD-115 (epoxy equivalent (weight): 180-194g/mol)
Epoxy Resin of Yueyang Petro-Chemical Industry General Plant
7. line style phenol formaldehyde (PF) Resins, epoxy F-51 (epoxy equivalent (weight): 185-195g/mol)
Epoxy Resin of Yueyang Petro-Chemical Industry General Plant
8. Move viscosity 3000mm
2The dimethyl silicone oil of/s (SH200)
Toray Dow Corning Silicone produces
9.C
8F
17SO
3Na
Wu Han sea DS chemical company produces
10. polyoxyethylene glycol (molecular weight 200)
Chemical plant, Dagu, Tianjin
11. ethylene glycol bisthioglycolate condenses
Chemical plant, Dagu, Tianjin
12 triethylamines
Shanghai chemical reagents corporation
13. toluene (technical grade)
Embodiment 1:
The 300ml deionized water is poured in the stainless steel vessel of 500ml, after adding the dissolving of the amino one type of silane coupling agent of 4gSH-6020 dispersed with stirring, add 40g ZEOSIL 200 wetting ability silicon-dioxide in stirring lentamente, at room temperature stirring reaction is after 40 minutes then, and reaction ends.The solids that filtration obtains is dry 16h under 60 ℃ vacuum.
In addition, agitator is being housed, is adding 3.3g TDI (2,4 and 2, the mixture of 6-tolylene diisocyanate) and 75ml toluene in three mouthfuls of glass flask of the 500ml of prolong, heating to 60-70 ℃ after the dispersed with stirring dissolving.In addition, in the beaker of 150ml, be added drop-wise in the above-mentioned flask in the 30min after adding 1.71g PEMP (1,2,2,6,6-pentamethyl--4-piperidines alcohol) and the 75ml toluene stirring and dissolving, react 2h down at 60 ℃.Add the dried silica that 2g dimethyl silicone oil SH-200 and 20g handled then, stir the 2h afterreaction down at 50-60 ℃ and end.Under 110 ℃, boil off toluene then, the solids that obtains under vacuum behind the dry 8h the light stability that contains hindered amine of embodiment 1 inorganic/organic composite microparticle 1.
Embodiment 2:
According to the method for embodiment 1,4.8g MDI (methylene diphenyl diisocyanate) is replaced the 3.3gTDI of embodiment 1, the light stability that contains hindered amine of embodiment 2 inorganic/organic composite microparticle 2.
Embodiment 3
According to the method for embodiment 1, with 0.4g C
8F
17SO
3Na replaces the 2g dimethyl silicone oil SH-200 of embodiment 1, the light stability that contains hindered amine of embodiment 3 inorganic/organic composite microparticle 3.
Embodiment 4
The 300ml deionized water is poured in the stainless steel vessel of 500ml, after adding the dissolving of the amino one type of silane coupling agent of 8gSH-6020 dispersed with stirring, add 40g ZEOSIL 200 wetting ability silicon-dioxide in stirring lentamente, at room temperature stirring reaction is after 40 minutes then, and reaction ends.The solids that filtration obtains is dry 16h under 60 ℃ vacuum.
In addition, agitator is being housed, is adding 6.7g bisphenol A type epoxy resin CYD-115,1.71g PEMP and 150ml toluene in three mouthfuls of glass flask of the 500ml of prolong, heating after the dispersed with stirring dissolving and under 70-80 ℃, react 2h.Add the dried silica that 2g dimethyl silicone oil SH-200 and 20g handled then, after stirring 2h under 70-80 ℃, reaction ends.Under 110 ℃, boil off toluene then, the solids that obtains under vacuum behind the dry 8h the light stability that contains hindered amine of embodiment 4 inorganic/organic composite microparticle 4.
Embodiment 5
The 300ml deionized water is poured in the stainless steel vessel of 500ml, after adding the dissolving of the amino one type of silane coupling agent of 6gSH-6020 dispersed with stirring, add 40g ZEOSIL 200 wetting ability silicon-dioxide in stirring lentamente, at room temperature stirring reaction is after 40 minutes then, and reaction ends.The solids that filtration obtains is dry 16h under 60 ℃ vacuum.
In addition, agitator is being housed, is adding 7.6g bisphenol A type epoxy resin CYD-115,1.71g PEMP and 150ml toluene in three mouthfuls of glass flask of the 500ml of prolong, heating after the dispersed with stirring dissolving and under 70-80 ℃, react 2h.Add the dried silica that 2g dimethyl silicone oil SH-200 and 20g handled then, after stirring 2h under 70-80 ℃, add 1.74gTDI again and stir 1h reaction end of a period.Under 110 ℃, boil off toluene then, the solids that obtains under vacuum behind the dry 8h the light stability that contains hindered amine of embodiment 5 inorganic/organic composite microparticle 5.
Embodiment 6
According to the method for embodiment 4, with 6.8g line style phenol formaldehyde (PF) Resins, epoxy F-51 replace embodiment 4 6.7g bisphenol A type epoxy resin CYD-115, the light stability that contains hindered amine of embodiment 6 inorganic/organic composite microparticle 6.Synthesizing of urethane (PU):
Agitator is being housed, is stirring behind polyoxyethylene glycol, 74g ethylene glycol bisthioglycolate condenses and the triethylamine 5g of adding 60g molecular weight 200 in three mouthfuls of glass flask of the 1000ml of prolong and heat to 50 ℃.The solution that 174g is dissolved in 200ml N,N-dimethylacetamide (DMAc) divide add for 3 times in the above-mentioned glass flask after, 50 ℃ down reaction 2h afterreactions end.Append 300ml DMAc again, the polyurethane solution that dilution generates.Polyurethane solution is cooled to room temperature and injects the 2000ml deionized water then, solid sediment with deionized water and methanol wash after, 40 ℃ of following vacuum-drying 16h.
The film making of 1-6 of the PU of embodiment:
Get above-mentioned 20g drying polyurethane and be dissolved in the polyurethane solution that gets 10wt% in the 180ml tetrahydrofuran (THF) (THF).With the light stability that contains hindered amine of embodiment inorganic/addition and polyurethane solution uniform mixing of organic composite microparticle 1-6 with solid polyurethane 1wt% after, boil off THF in the glassware that reinjects, the PU that promptly the obtains embodiment 1-6 1-6 that films.
The film making of 1-6 of the Resins, epoxy of embodiment (EP):
Inorganic/organic composite microparticle the 1-6 that contains hindered amine structure of embodiment is joined among the bisphenol A type epoxy resin CYD-115 with the addition of 1wt%, after adding the diethylenetriamine and an amount of ethanol uniform mixing of 9.5wt% of amount of resin again, the dry solidification in the glassware that reinjects, the EP that promptly the obtains embodiment 1-6 1-6 that films.
Comparative example 1:
The polyurethane solution of 10wt% injects glassware and boils off-1 (PU) that film that obtains comparative example 1 behind the THF.
Comparative example 2:
Addition with the 0.1wt% of solid polyurethane in the polyurethane solution of 10wt% adds PEMP, evenly injects glassware after the blend and boils off THF, promptly obtains-2 (PU) that film of comparative example 2.
Comparative example 3:
Inject the glassware dry solidification behind the diethylenetriamine of adding amount of resin 9.5wt% and the adequate amount of ethanol uniform mixing among the bisphenol A type epoxy resin CYD-115, promptly obtain-3 (EP) that film of comparative example 3.
Comparative example 4:
After adding the diethylenetriamine and adequate amount of ethanol uniform mixing of PEMP, 9.5wt% of amount of resin 0.1wt% among the bisphenol A type epoxy resin CYD-115, dry solidification in the glassware that reinjects promptly obtains-4 (EP) that film of comparative example 4.The light stability test that PU films and EP films:
The PU of embodiment 1-6 1-6, EP 1-6 and the comparative example 1-4 that films that films that films was placed on outdoor environment following 6 months, and filming is subjected to the surface observation behind the natural light irradiation as shown in table 1.
Table 1
| Example | ??No. | ??PEMP *1Residue content or PEMP content (%) | Variable color | Crackle | ||
| PU films | EP films | PU films | EP films | |||
| ????1 | ????0.059 | ?A | ??A | ??A | ??A | |
| ????2 | ????0.056 | A | ??A | ??A | ??A | |
| Embodiment | ??3 | ????0.062 | ????A | ????A | ????A | ????A |
| ??4 | ????0.050 | ????A | ????A | ????A | ????A | |
| ??5 | ????0.047 | ????B | ????A | ????A | ????A | |
| ??6 | ????0.050 | ????A | ????A | ????A | ????A | |
| Comparative example | ??1 | ????0 | ????D | ????D | ||
| ??2 | ????0.10 | ????B | ????A | |||
| ??3 | ????0 | ????D | ????C | |||
| ??4 | ????0.10 | ????A | ????A |
* 1: 1,2,2,6,6-pentamethyl--4-piperidines alcohol
A. the surface is good; B. the surface better; C. surperficial relatively poor; D. the surface analysis that surperficial extreme difference is filmed:
The embodiment PU that at room temperature placed 3 months film 1,3 and EP film and 1,3 analyze its surface-element composition through x-ray photoelectron spectroscopy (XPS), all present Si at the 102eV place
2pXPS spectrum.
Claims (10)
1. the light stability that contains hindered amine is inorganic/preparation method of organic composite microparticle, it is characterized in that it comprises the steps: 1). use the scope of the represented amino one type of silane coupling agent treatment median size of general expression (1) at 0.01-30 μ m
H
2N-(R
1-NH)
n-R
2-Si-(R
3) (R
4) (R
5) (1) interior wetting ability silicon-dioxide;
In the formula (1): R
1, R
2Be respectively the alkyl that the charcoal atomicity is 1-4, R
3, R
4, R
5Be respectively hydrogen atom, the charcoal atomicity is alkyl, the siloxy of 1-3, n is the integer of 0-5; The consumption of amino one type of silane coupling agent is the 3-40wt% of wetting ability silicon-dioxide, and amino one type of silane coupling agent is made the amino one type of silane coupling agent aqueous solution that concentration is 0.5-3wt%; The reaction times of amino one type of silane coupling agent and wetting ability silicon-dioxide is 5-100 minute, filters the solids dry 15-17h under 35-65 ℃ vacuum that obtains, and gets product 1;
2). represented piperidinol type hindered amine compound of general expression (2) and one of following three kinds reaction then, a. diisocyanate compound, b. Resins, epoxy, c. diisocyanate compound and Resins, epoxy, product 2;
Y is the alkyl of charcoal atomicity 1-18 in the formula (2), and the addition of piperidinol type hindered amine compound is the 1-30wt% of wetting ability silicon-dioxide; If when adopting the reaction of piperidinol type hindered amine compound and diisocyanate compound, must in non-proton organic solvent, carry out, at 40-70 ℃ temperature range internal reaction 2-3h, the equivalence ratio of its piperidinol type hindered amine compound and diisocyanate compound is 1: 1.5-3.5; If when adopting the reaction of piperidinol type hindered amine compound and Resins, epoxy, reaction must be carried out in non-proton organic solvent, at 70-90 ℃ temperature range internal reaction 2-3h, the equivalence ratio of piperidinol type hindered amine compound and Resins, epoxy is 1: 1.5-3.5; If when adopting the mixture reaction of piperidinol type hindered amine compound and diisocyanate compound and Resins, epoxy, piperidinol type hindered amine compound and diisocyanate compound are 1 with the equivalence ratio of mixing of Resins, epoxy: 1.5-3.5, wherein, the equivalence ratio of diisocyanate compound and Resins, epoxy is arbitrarily.
3). with product 2 and product 1 reaction; Step 2) if when adopting piperidinol type hindered amine compound and diisocyanate compound, temperature of reaction is at 90-110 ℃ of scope internal reaction 2-10h in, and component distillation is removed non-proton organic solvent and water, product; Step 2) if when adopting piperidinol type hindered amine compound and Resins, epoxy, at 70-90 ℃ temperature range internal reaction 2-3h, component distillation is removed non-proton organic solvent and water in, product; If when adopting the reaction of piperidinol type hindered amine compound and diisocyanate compound and Resins, epoxy, at 70-90 ℃ temperature range internal reaction 2-3h, component distillation is removed non-proton organic solvent and water, get product.
2. the light stability that contains hindered amine according to claim 1 is inorganic/preparation method of organic composite microparticle, it is characterized in that: described step 1) or step 2) in can add organic silicone oil or modification organic silicon oil, kinetic viscosity is generally at 1-10 ten thousand mm
2In/s the scope, addition is the 0.5-5wt% of wetting ability silicon-dioxide.
3. the light stability that contains hindered amine according to claim 1 is inorganic/preparation method of organic composite microparticle, it is characterized in that: described step 1) or step 2) in can add the fluorinated interfacial agent, addition is the 0.1-2wt% of wetting ability silicon-dioxide.
4. the light stability that contains hindered amine according to claim 1 is inorganic/preparation method of organic composite microparticle, and it is characterized in that: described non-proton organic solvent is toluene or dimethylbenzene.
5. the light stability that contains hindered amine according to claim 1 is inorganic/preparation method of organic composite microparticle, and it is characterized in that: described diisocyanate compound is aliphatic diisocyanate and the aromatic diisocyanate of carbonatoms 4-20.
6. the light stability that contains hindered amine according to claim 5 is inorganic/preparation method of organic composite microparticle, it is characterized in that: described diisocyanate compound is a hexamethylene diisocyanate, 2,4-or 2,6-tolylene diisocyanate or naphthalene diisocyanate.
7. the light stability that contains hindered amine according to claim 1 is inorganic/preparation method of organic composite microparticle, and it is characterized in that: described wetting ability silicon-dioxide median size is 0.01-20 μ m.
8. the light stability that contains hindered amine according to claim 1 is inorganic/preparation method of organic composite microparticle, and it is characterized in that: the reaction times of described amino one type of silane coupling agent and wetting ability silicon-dioxide is 20-60 minute.
9. the light stability that contains hindered amine according to claim 1 is inorganic/preparation method of organic composite microparticle, and it is characterized in that: the consumption of described amino one type of silane coupling agent is the 5-20wt% of wetting ability silicon-dioxide.
10. the light stability that contains hindered amine according to claim 1 is inorganic/preparation method of organic composite microparticle, and it is characterized in that: described Resins, epoxy is glycidyl ether based epoxy resin, glycidyl ester based epoxy resin class, Racemic glycidol amine epoxy resin, aliphatic epoxy compound or alicyclic epoxide compound.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB2005100184398A CN1296416C (en) | 2005-03-24 | 2005-03-24 | Method for preparing light stable composite inorganic/organic corpuscles containing hindered amine |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB2005100184398A CN1296416C (en) | 2005-03-24 | 2005-03-24 | Method for preparing light stable composite inorganic/organic corpuscles containing hindered amine |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1687202A true CN1687202A (en) | 2005-10-26 |
| CN1296416C CN1296416C (en) | 2007-01-24 |
Family
ID=35305244
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CNB2005100184398A Expired - Fee Related CN1296416C (en) | 2005-03-24 | 2005-03-24 | Method for preparing light stable composite inorganic/organic corpuscles containing hindered amine |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN1296416C (en) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1331589C (en) * | 2005-11-01 | 2007-08-15 | 浙江大学 | Layer-by-layer microcapsule assembling process based on mutual covalent action |
| CN104312215A (en) * | 2014-09-22 | 2015-01-28 | 太原理工大学 | Silicon dioxide surface grafting modification method |
| CN106589574A (en) * | 2015-10-16 | 2017-04-26 | 奕益实业有限公司 | Method for preparing composite wood and composite wood |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100567393C (en) * | 2008-03-20 | 2009-12-09 | 江南大学 | A kind of surface modified spherical SiO 2The preparation method of particulate epoxy resin composite material |
Family Cites Families (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6071614A (en) * | 1997-07-14 | 2000-06-06 | 3M Innovative Properties Company | Microporous fluorinated silica agglomerate and method of preparing and using same |
| US6646022B2 (en) * | 2000-07-05 | 2003-11-11 | Mitsubishi Rayon Co., Ltd. | Photocuring resin compositions, photocuring sheets and molded article using the same, and processes of production thereof |
-
2005
- 2005-03-24 CN CNB2005100184398A patent/CN1296416C/en not_active Expired - Fee Related
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1331589C (en) * | 2005-11-01 | 2007-08-15 | 浙江大学 | Layer-by-layer microcapsule assembling process based on mutual covalent action |
| CN104312215A (en) * | 2014-09-22 | 2015-01-28 | 太原理工大学 | Silicon dioxide surface grafting modification method |
| CN104312215B (en) * | 2014-09-22 | 2016-03-09 | 太原理工大学 | A kind of surface graft modification method of silicon-dioxide |
| CN106589574A (en) * | 2015-10-16 | 2017-04-26 | 奕益实业有限公司 | Method for preparing composite wood and composite wood |
Also Published As
| Publication number | Publication date |
|---|---|
| CN1296416C (en) | 2007-01-24 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN1304462C (en) | Silicon based quaternary ammonium functional compositions and methods for making them | |
| CN1168761C (en) | Addition cross-linked epoxy functional organo-siloxanes polymer and coating composition | |
| CN1125841C (en) | Epoxy resin composition and process for producing silane-modified epoxy resin | |
| CN101050223A (en) | Tripolymer in isocyanic ester class modified by silicane or functional polusiloxane, preparation method | |
| CN1747985A (en) | Silicon compound containing epoxy group and thermosetting resin composition | |
| CN1752163A (en) | A kind of aqueous epoxide resin paint and preparation method thereof | |
| CN1867612A (en) | Nanocomposites based on polyurethane or polyurethane-epoxy hybrid resins prepared avoiding isocyanates | |
| CN1296416C (en) | Method for preparing light stable composite inorganic/organic corpuscles containing hindered amine | |
| US10913823B2 (en) | POSS-based polyurethane modified poly(propylene carbonate) and preparation method thereof | |
| CN1257206C (en) | Low viscosity curing agents compositions in epoxy resin systems for low temperature cure applications | |
| CN1626537A (en) | Multi-functional cyclic silicate compound, siloxane-based polymer prepared from the compound and process of producing insulating film using the polymer | |
| CA2918266A1 (en) | Acid suppressible rheology modifier stabilized with phosphoric acid ester surfactant | |
| CN1958639A (en) | Solidifying agent for aqueous epoxy resin, and preparation method | |
| CN104892922B (en) | A kind of Based On Hydroxy-terminated Polyepichlorohydrin and preparation method thereof | |
| JP4457783B2 (en) | Curable resin composition | |
| EP1876198B1 (en) | Process for preparing amino-functional siloxanes | |
| CN1621481A (en) | Epoxy resin composition for encapsulating optical semiconductor element and optical semiconductor device using the same | |
| CN1944481A (en) | Process for preparing acrylate resin for powder paint | |
| CN1522318A (en) | Spandex containing quaternary amine additives | |
| JP2006249160A (en) | Sulfonated polyorganosilsesquioxane and its preparation method | |
| CN1308401C (en) | Method for preparing hydrophobic inorganic and organic composite corpuscle | |
| CN1894300A (en) | Synthesis of acylureas and composition comprising acylureas | |
| KR101811163B1 (en) | A cycloaliphatic resin, method for obtaining the same and its application in a high resistance coating | |
| CN113527118B (en) | Normal-temperature water-based epoxy curing agent and preparation method and application thereof | |
| CN101659741A (en) | Epoxy resin toughening curing agent and preparation method thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant | ||
| C17 | Cessation of patent right | ||
| CF01 | Termination of patent right due to non-payment of annual fee |
Granted publication date: 20070124 |