CN107987312A - A kind of preparation method of light stabilizer, light aging resisting PP composite material - Google Patents
A kind of preparation method of light stabilizer, light aging resisting PP composite material Download PDFInfo
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- CN107987312A CN107987312A CN201711287224.5A CN201711287224A CN107987312A CN 107987312 A CN107987312 A CN 107987312A CN 201711287224 A CN201711287224 A CN 201711287224A CN 107987312 A CN107987312 A CN 107987312A
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G53/00—Compounds of nickel
- C01G53/006—Compounds containing, besides nickel, two or more other elements, with the exception of oxygen or hydrogen
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2002/00—Crystal-structural characteristics
- C01P2002/70—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data
- C01P2002/72—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data by d-values or two theta-values, e.g. as X-ray diagram
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/01—Particle morphology depicted by an image
- C01P2004/03—Particle morphology depicted by an image obtained by SEM
Abstract
The present invention relates to a kind of preparation method of new light stabilizer, and the light aging resisting PP composite material with the light stabilizer obtained by the preparation method.The general formula of the light stabilizer obtained through the preparation method is expressed as [M (II)1‑xM(Ⅲ)x(OH)2]x+Ax/n n‑·mH2O, wherein, M (II) is bivalent metal ion Mg2+And Ni2+, M (III) is trivalent metal ion Al3+, A is the anion that valence state is n valencys, and x is the molar ratio of M (III) and [M (III)+M (II)], and m is to crystallize water, x=0.1~0.5, A OH‑、CO3 2‑, m=0~10.The present invention solves the problems, such as to need in layered double-hydroxide Intercalation reaction organic uv absorbers to obtain light stabilizer, so as to obtain the preferable light aging resisting PP composite material of stability.
Description
Technical field
The invention belongs to materials chemistry, chemical technology field, is related to a kind of preparation method of light stabilizer and has and is somebody's turn to do
The light aging resisting PP composite material of light stabilizer.
Background technology
Polypropylene (PP) is widely used in chemical industry, building materials, car and boat etc. because it has the advantages that heat-resisting, easy processing, light weight
Engineering field.PP Materials trend shows that PP is widely used in outdoor at present, as exterior decorative materials, auto parts and components,
The plastic seat in stadium etc..But as high molecular material PP as other high molecular polymers, when being chronically exposed to outdoor
When can change, such as product surface cracking, gloss forfeiture, yellowing, relative molecular mass decline, can more seriously lead
The mechanical properties such as impact strength, elongation at break, tensile strength, bending strength are caused significantly to decline so as to influence PP products just
Often use.PP causes the factor of aging very much, the dirt in temperature, precipitation, humidity and air exposed to outdoor meeting accelerated ageing
Dye thing and ozone etc. are responsible for the aging of material.But the main reason for aging is the energy that PP materials absorb ultraviolet light, is drawn
Auto-oxidation reaction is sent out, so as to cause light degradation occurs so that product local appearance and physical mechanical property are deteriorated.Therefore occur
One urgent problem：The PP materials of outdoor application have to the performance with certain ageing resistance by ultraviolet light.Therefore,
The PP materials with ageing resistance by ultraviolet light become the hot spot studied both at home and abroad.To obtain ageing-resistant performance preferable poly- third
Alkene composite material, people usually promote its weatherability by means of adding stabilizer and antioxidant, and this method is relatively simple
It is feasible, and method most realistic, most widely used at present, and achieve preferable effect.
The current research in relation to layered metal hydroxides light stabilizer is mainly concentrated through the replaceable of interlayer anion
Property, the anion interlayer materials such as salicylic acid esters, benzophenone, Hinered phenols are introduced, so that stratiform light stabilizer is obtained, and
By varying the element species and ratio of cation laminate, stability height, the double hydrogen-oxygens of the strong stratiform of uv absorption capacity are prepared
Compound class light stabilizer is then reported less.
The content of the invention
The present invention provides a kind of preparation method of light stabilizer and the light aging resisting polypropylene material with the light stabilizer.
A kind of preparation method of light stabilizer, the general formula of the light stabilizer are expressed as [M (II)1-xM(Ⅲ)x(OH)2]x+
Ax/n n-·mH2O, wherein, M (II) is bivalent metal ion Mg2+And Ni2+；M (III) is trivalent metal ion Al3+；A is valence state
For the anion of-n valencys；X is the molar ratio of M (III) and [M (III)+M (II)]；M is hydration water number, and x=0.1~0.5, A are
OH-、CO3 2-, m=0~10；The preparation method comprises the following steps：
A, it is the soluble-salt of divalence magnesium ion, bivalent nickel ion and trivalent aluminium ion is soluble in water, it is dense to be made into cation
Salting liquid of the degree less than 1.0mol/L, wherein bivalent cation mole are more than the 60% of total cation mole；
B, urea is added in this salting liquid and obtains mixed solution, the wherein molar concentration of urea is divalent metal
0.5~3.0 times of molar concentration；
C, this mixed solution is transferred in reaction kettle, is cooled to room temperature after hydro-thermal reaction 0.5h~48h, filtered,
Washing, the product drying after washing up to light stabilizer described in right 1.
Further, the step A middle-jiao yang, function of the spleen and stomach ion concentration range is 0.1mol/L~1.0mol/L.
Further, cation mole is more than the 80% of total cation mole in the step A.
Further, the molar concentration of urea is the 1.0~2.0 of divalent metal molar concentration in the step B
Times.
Further, the hydrothermal temperature of the step C is 100 DEG C~200 DEG C.
Further, the step C drying conditions are 80 DEG C~120 DEG C dry 4h~12h.
A kind of light aging resisting PP composite material, light stabilizer obtained above is added in polypropylene, through being kneaded
Afterwards up to the PP composite material of light aging resisting, the wherein mass fraction of light stabilizer is composite material total mass fraction
0.05%~10%.
The present invention has the following advantages compared with prior art：
1st, technique is simple, easy to operate, and flow is short, and production cost is low, equipment material is required relatively low；
2nd, need not be added in reaction process additive and anion ultraviolet absorber, barrier etc. can produce containing
The light stabilizer and polypropylene light aging resisting composite products of magnesium nickel aluminium.
Brief description of the drawings
Below in conjunction with accompanying drawings and embodiments, the invention will be further described, in attached drawing：
Fig. 1 is the XRD spectra of 1 light stabilizer of the embodiment of the present invention
Fig. 2 is the XRD spectra of 2 light stabilizer of the embodiment of the present invention
Fig. 3 is the XRD spectra of 3 light stabilizer of the embodiment of the present invention
Fig. 4 is that the SEM of 4 light stabilizer of the embodiment of the present invention schemes；
Fig. 5 is the XRD spectra of 4 light stabilizer of the embodiment of the present invention；
Fig. 6 is 4 light aging resisting PP composite material of the embodiment of the present invention under different light stabilizer additive amounts during aging
Between with tensile strength graph of a relation.
Embodiment
With reference to embodiment, the invention will be further described.
Embodiment 1
The soluble divalence that uses, the salt of trivalent metal cation is magnesium nitrate hexahydrate (Mg (NO3)2·6H2O), six water nitre
Sour nickel (Ni (NO3)2·6H2) and nine water aluminum nitrate (Al (NO O3)3·9H2O)。
Weigh the beaker that 5.77g magnesium nitrate hexahydrates, six water nickel nitrates of 6.54g and nine water aluminum nitrates of 12.66g are put into 200mL
In, 150mL secondary waters are added, stirring is completely dissolved it.
With weighing 12.16g urea (H2NCONH2), it is added in salting liquid, is transferred to hydrothermal reaction kettle until completely dissolved
In, react 8h at 140 DEG C.
Natural cooling after taking-up, is filtered, washing, at 80 DEG C in constant temperature blast drying oven dry 8h, grinding, after sieving i.e.
The light stabilizer product of magnesium ferronickel must be contained.
Embodiment 2
The soluble divalence that uses, the salt of trivalent metal cation is magnesium nitrate hexahydrate (Mg (NO3)2·6H2O), six water nitre
Sour nickel (Ni (NO3)2·6H2) and nine water aluminum nitrate (Al (NO O3)3·9H2O)。
Weigh the beaker that 5.77g magnesium nitrate hexahydrates, six water nickel nitrates of 6.54g and nine water aluminum nitrates of 12.66g are put into 200mL
In, 150mL secondary waters are added, stirring is completely dissolved it.
With weighing 6.08g urea (H2NCONH2), it is added in salting liquid, is transferred to until completely dissolved in hydrothermal reaction kettle,
4h is reacted at 160 DEG C.
Natural cooling after taking-up, is filtered, washing, at 80 DEG C in constant temperature blast drying oven dry 8h, grinding, after sieving i.e.
The light stabilizer product of magnesium ferronickel must be contained.
Embodiment 3
The soluble divalence that uses, the salt of trivalent metal cation is magnesium nitrate hexahydrate (Mg (NO3)2·6H2O), six water nitre
Sour nickel (Ni (NO3)2·6H2) and nine water aluminum nitrate (Al (NO O3)3·9H2O)。
Weigh the beaker that 4.51g magnesium nitrate hexahydrates, six water nickel nitrates of 2.60g and nine water aluminum nitrates of 3.39g are put into 200mL
In, 150mL secondary waters are added, stirring is completely dissolved it.
With weighing 2.16g urea (H2NCONH2), it is added in salting liquid, is transferred to until completely dissolved in hydrothermal reaction kettle,
48h is reacted at 100 DEG C.
Natural cooling after taking-up, is filtered, washing, at 80 DEG C in constant temperature blast drying oven dry 8h, grinding, after sieving i.e.
The light stabilizer product of magnesium ferronickel must be contained.
Embodiment 4
The soluble divalence that uses, the salt of trivalent metal cation is magnesium nitrate hexahydrate (Mg (NO3)2·6H2O), six water nitre
Sour nickel (Ni (NO3)2·6H2) and nine water aluminum nitrate (Al (NO O3)3·9H2O)。
Weigh the beaker that 11.53g magnesium nitrate hexahydrates, six water nickel nitrates of 6.54g and nine water aluminum nitrates of 8.43g are put into 200mL
In, 150mL secondary waters are added, stirring is completely dissolved it.
With weighing 10.13g urea (H2NCONH2), it is added in salting liquid, is transferred to hydrothermal reaction kettle until completely dissolved
In, react 12h at 120 DEG C.
Natural cooling after taking-up, is filtered, washing, at 80 DEG C in constant temperature blast drying oven dry 8h, grinding, after sieving i.e.
The light stabilizer product of magnesium ferronickel must be contained.
Above-mentioned gained light stabilizer is added in polypropylene, up to light aging resisting polypropylene composite materials material after 180 DEG C are kneaded
Material.Wherein additive amount of the light stabilizer in corresponding light aging resisting PP composite material is respectively 1%, 2%, 4%, 6%；
The ageing time of the corresponding four kinds of light aging resisting PP composite materials obtained is contrasted with tensile strength relation, while with
The polypropylene material for being not added with light stabilizer acquisition is contrasted as a comparison case；Comparing result is as shown in Figure 6.Can from Fig. 6
To find out, polyacrylic light aging resisting property can be significantly improved by adding the light stabilizer.
Claims (7)
1. a kind of preparation method of light stabilizer, it is characterised in that the general formula of the light stabilizer is expressed as [M (II)1-xM(Ⅲ)x
(OH)2]x+Ax/n n-·mH2O, wherein, M (II) is bivalent metal ion Mg2+And Ni2+；M (III) is trivalent metal ion Al3+；A
It is the anion that valence state is-n valencys；X is the molar ratio of M (III) and [M (III)+M (II)]；M is to be hydrated water number, x=0.1~0.5,
A is OH-、CO3 2-, m=0~10；The preparation method comprises the following steps：
A, it is the soluble-salt of divalence magnesium ion, bivalent nickel ion and trivalent aluminium ion is soluble in water, it is small to be made into cation concn
In the salting liquid of 1.0mol/L, wherein bivalent cation mole is more than the 60% of total cation mole；
B, urea is added in this salting liquid and obtains mixed solution, the wherein molar concentration of urea is divalent metal mole
0.5~3.0 times of concentration；
C, this mixed solution is transferred in reaction kettle, is cooled to room temperature after hydro-thermal reaction 0.5h~48h, filtered, washing,
The product drying after washing up to light stabilizer described in right 1.
2. preparation method according to claim 1, it is characterised in that the step A middle-jiao yang, function of the spleen and stomach ion concentration ranges are
0.1mol/L~1.0mol/L.
3. preparation method according to claim 1, it is characterised in that cation mole is more than total sun in the step A
The 80% of ion mole.
4. preparation method according to claim 1, it is characterised in that the molar concentration of urea is divalence in the step B
1.0~2.0 times of metal cation molar concentration.
5. preparation method according to claim 1, it is characterised in that the hydrothermal temperature of the step C for 100 DEG C~
200℃。
6. preparation method according to claim 1, it is characterised in that the step C drying conditions are dry for 80 DEG C~120 DEG C
Dry 4h~12h.
7. a kind of light aging resisting PP composite material, it is characterised in that by any preparation method systems of claim 1-6
The light stabilizer obtained is added in polypropylene, up to light aging resisting PP composite material after mixing, wherein, described fast light
In aging PP composite material, the mass fraction of the light stabilizer is 0.05%~10%.
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| CN201711287224.5A CN107987312A (en) | 2017-12-07 | 2017-12-07 | A kind of preparation method of light stabilizer, light aging resisting PP composite material |
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| CN201711287224.5A CN107987312A (en) | 2017-12-07 | 2017-12-07 | A kind of preparation method of light stabilizer, light aging resisting PP composite material |
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Citations (6)
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|---|---|---|---|---|
| CN1615312A (en) * | 2002-01-11 | 2005-05-11 | 桑诺克公司(R&M) | Synthetic hydrotalcites, syntheses and uses |
| CN1962453A (en) * | 2006-11-22 | 2007-05-16 | 天津化工研究设计院 | Process for producing hydrotalcite-like layered hydroxide |
| CN101759213A (en) * | 2010-01-05 | 2010-06-30 | 北京化工大学 | Method for preparing layered bimetal hydroxide by using metallic powder |
| CN101774548A (en) * | 2010-03-15 | 2010-07-14 | 北京泰克来尔科技有限公司 | Recycling technology of mother solution obtained by preparing layered composition metal hydroxide by coprecipitation method |
| CN103694552A (en) * | 2012-09-28 | 2014-04-02 | 中国石油天然气股份有限公司 | Thermo-oxidative aging resistant polypropylene composition and preparation method thereof |
| CN105419064A (en) * | 2015-12-31 | 2016-03-23 | 北京泰克来尔科技有限公司 | Laminated composite metal hydroxide and multifunctional master batch preparation method thereof |
-
2017
- 2017-12-07 CN CN201711287224.5A patent/CN107987312A/en active Pending
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1615312A (en) * | 2002-01-11 | 2005-05-11 | 桑诺克公司(R&M) | Synthetic hydrotalcites, syntheses and uses |
| CN1962453A (en) * | 2006-11-22 | 2007-05-16 | 天津化工研究设计院 | Process for producing hydrotalcite-like layered hydroxide |
| CN101759213A (en) * | 2010-01-05 | 2010-06-30 | 北京化工大学 | Method for preparing layered bimetal hydroxide by using metallic powder |
| CN101774548A (en) * | 2010-03-15 | 2010-07-14 | 北京泰克来尔科技有限公司 | Recycling technology of mother solution obtained by preparing layered composition metal hydroxide by coprecipitation method |
| CN103694552A (en) * | 2012-09-28 | 2014-04-02 | 中国石油天然气股份有限公司 | Thermo-oxidative aging resistant polypropylene composition and preparation method thereof |
| CN105419064A (en) * | 2015-12-31 | 2016-03-23 | 北京泰克来尔科技有限公司 | Laminated composite metal hydroxide and multifunctional master batch preparation method thereof |
Non-Patent Citations (2)
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| 刘漫红 等编著: "《纳米材料及其制备技术》", 31 August 2014, 冶金工业出版社 * |
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