CN101362858A - Magnetic silicate clay/polyamide compound resin - Google Patents
Magnetic silicate clay/polyamide compound resin Download PDFInfo
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- CN101362858A CN101362858A CNA2008102007279A CN200810200727A CN101362858A CN 101362858 A CN101362858 A CN 101362858A CN A2008102007279 A CNA2008102007279 A CN A2008102007279A CN 200810200727 A CN200810200727 A CN 200810200727A CN 101362858 A CN101362858 A CN 101362858A
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Abstract
The invention relates to a compound resin of magnetic silicate clay/daiamid. The compound resin is mainly obtained after in situ polymerization by 100 portions of acid amides by weight and 0.05 to 0.10 portion of magnetic silicate clay by weight under the existing condition of a catalyst and an external magnetic field; wherein, the magnetic silicate clay refers to meerschaum, paligorskite, montmorillonite or attapulgite which is loaded with magnetic matters; the charge number of the magnetic matters is as follows: 5 to 10 portions of the magnetic matters are loaded by 100 portions of the meerschaum, the paligorskite, the montmorillonite or the attapulgite. Compared with the existing modified compound resin of daiamid, the mechanical properties (in particular to the notch impact strength) of the compound resin are increased and the processing property thereof is improved.
Description
Technical field
The present invention relates to a kind of compound resin of polymeric amide, specifically, relate to a kind of magnetic silicate clay/polyamide compound resin.
Background technology
Polymeric amide (has another name called: nylon) be a kind of engineering plastics of knowing for people.Because polymeric amide exists rigidity and thermotolerance is not good, reach the more high defective of water-intake rate (making the stability and the electrical property variation of its goods), has limited the Application Areas of polymeric amide.Therefore, the modification problem of polymeric amide enjoys chemists' concern.
CN 1687184A discloses a kind of through low-dimensional nano clay modified " polymeric amide/low-dimensional nanoclay compound resin ", though the performance of this compound resin improves (corresponding polymeric amide), it still has room for improvement.
Summary of the invention
The present invention adopts magnetic silicate clay as properties-correcting agent, under action of alternating magnetic field, makes magnetic silicate clay and acid amides (monomer) get magnetic silicate clay/polyamide compound resin (or claiming modified polyamide resin) behind in-situ polymerization.
The present invention makes inorganic particulate (properties-correcting agent) form ordered arrangement at microcosmic by the action of a magnetic field, impels high molecular nucleation degree and crystallization velocity.Prepared compound resin, its microcosmic crystalline structure is more orderly, compares with existing modified polyamide compound resin, has improved the mechanical property (particularly notched Izod impact strength) of compound resin and has improved its processing characteristics.
The said magnetic silicate clay/polyamide compound resin of the present invention, it is mainly by the acid amides (monomer) of 100 parts by weight and the magnetic silicate clay of 0.05 parts by weight～0.10 parts by weight, having under catalyzer and the externally-applied magnetic field existence condition, behind in-situ polymerization, obtain.
Wherein: said acid amides (monomer) is meant: the corresponding amide monomer that can obtain existing polymeric amide (or claiming nylon) resin [as (but being not limited to): nylon-6, nylon-46, nylon-9, nylon-11, PA-12, nylon-66, nylon-610, nylon-6 12 or nylon-1010 etc.] by polymerization;
Silicate clay involved in the present invention is meant: [the experience molecular formula is sepiolite: Mg
8(H
2O)
4(Si
6O
15) (OH)
48H
2O], [the experience molecular formula is polygorskite: Mg
5(H
2O)
4(Si
4O
10) (OH)
2], montmorillonite (polynite) [the experience molecular formula is: (Na, Ca)
0.33(Al, Mg)
2(Si
4O
10) (OH)
2NH
2O] or attapulgite [the experience molecular formula is: Si
8Mg
5O
20(OH)
2(OH
2)
44H
2O], the particle diameter of said silicate clay is preferred 200 orders～400 orders;
Said magnetic silicate clay is meant: load (or claiming absorption) material that is magnetic is (as γ-Fe
2O
3, Fe
3O
4, CrO
2And/or Co (OH)
2-γ-Fe
2O
3) sepiolite, polygorskite, montmorillonite (polynite) or attapulgite, magnetic substance load (absorption) amount is: the magnetic substance of the sepiolite of 100 parts by weight, polygorskite, montmorillonite (polynite) or attapulgite load (absorption) 5 parts by weight～10 parts by weight.
In an optimal technical scheme of the present invention, used acid amides (monomer) is: hexanolactam.
In another optimal technical scheme of the present invention, used magnetic silicate clay is: load (absorption) Fe
3O
4Montmorillonite (polynite) or attapulgite.
Description of drawings
Fig. 1: the SEM figure that handles attapulgite clay for high temperature and acid activation among the embodiment 1.
Fig. 2: for having the attapulgite clay/Fe of target characterization of adsorption among the embodiment 3
3O
4Composite granule SEM figure.
Fig. 3: be the polymeric amide/magnetic silicate clay matrix material section TEM figure that has the orientation characteristic among the embodiment 1.
Embodiment
A kind of method for preparing the said magnetic silicate clay/polyamide compound resin of the present invention comprises the steps:
(1) preparation of magnetic silicate clay:
Will be through the silicate clay of 100 parts by weight of high temperature pre-treatment (promptly under 250 ℃～400 ℃ states keep 1.5-3 hour) and the inorganic acid (example hydrochloric acid of 10 parts by weight～20 parts by weight, sulfuric acid or nitric acid etc.) mix, the mixture that gained is made up of silicate clay and inorganic acid keeps (ageing) in 1 hour～6 hours under 80 ℃～100 ℃ conditions, add the dispersion agent of 3 parts by weight～5 parts by weight and the nucleation control agent of 1 parts by weight～3 parts by weight to this system, under rotating speed 3000r/min～8000r/min condition high-speed stirring 10 minutes～15 minutes suspension, again with the magnetic substance of this suspension and 5 parts by weight～10 parts by weight (as Fe
3O
4) mix, high-speed stirring got magnetic silicate clay in 10 minutes～20 minutes under rotating speed 3000r/min～8000r/min condition;
(2) preparation of magnetic silicate clay/polyamide compound resin (target compound):
With the activator of the catalyzer of the magnetic silicate clay [making] of the amide monomer (as hexanolactam etc.) of 100 parts by weight, 0.05 parts by weight～0.10 weight part, 0.5 parts by weight～5 parts by weight and 0.1 parts by weight～3 parts by weight by step (1) under 70 ℃～120 ℃ and vacuum condition, dewatered 30 minutes～90 minutes, be placed on temperature then and be in the reactor in 150 ℃～280 ℃ and 80mT～100mT magnetic field, reacted 10 minutes～20 minutes target compound (polymeric amide/magnetic silicate clay compound resin).
Wherein: said dispersion agent is: the mixture of one or more in acrylic acid or the like or the phosphoric acid salt dispersion agent;
Said nucleation control agent is: one or more in weak acid (as phosphoric acid or citric acid) or its esters;
Said catalyzer is: sodium hydroxide or/and sodium for hexanolactam;
Said activator is: diphenylmethanediisocyanate (MDI) is or/and tolylene diisocyanate (TDI).
The present invention is further illustrated below by embodiment, and its purpose only is better to understand content of the present invention, so protection scope of the present invention is not limited by the cases cited.
Embodiment 1
1. Attapulgite suspension preparation component (in parts by weight, letter meter " part ") is handled in pyroprocessing and acid activation:
(1) Attapulgite original soil (400 order) is 100 parts
(2) sulfuric acid (10v/v%) is 10 parts
(3) dispersion agent is 3 parts
2. Attapulgite/Fe
3O
4The magnetic composite powder raw material is formed (in parts by weight, letter meter " part "):
(1) pyroprocessing and acid activation Attapulgite are 100 parts
(2) ultra-fine Fe
3O
4(commercially available) 5 parts
(3) citric acid (nucleation control agent) is 1 part
3. the raw material of polymeric amide/magnetic Attapulgite matrix material is formed (in parts by weight, letter meter " part "):
(1) hexanolactam is 100 parts
(2) magnetic Attapulgite composite granule is 0.10 part
(3) sodium is for 2.0 parts of hexanolactams
(4) TDI is 0.5 part
4. working method:
With Attapulgite original soil 400 ℃ of pyroprocessing 2 hours in retort furnace, be cooled to that to add concentration after the room temperature be the sulfuric acid of 10v/v%, reacted 30 minutes, 100 ℃ activate 2 hours in baking oven, vacuum filtration obtains high-specific surface area attapulgite filter cake, being washed to the pH value is 7, oven dry is also pulverized, press high temperature and acid activation and handle attapulgite, sodium polyacrylate (dispersion agent), quality is than being the mixed of 100:3:1000, uses emulsification pretreatment stirrer high-speed stirring 10 minutes under the rotating speed of 4000r/min～6000r/min, obtains pyroprocessing acid activation Attapulgite suspension.
According to Attapulgite/Fe
3O
4Proportioning during the magnetic composite powder raw material is formed will be through Attapulgite suspension, the Fe of pyroprocessing and acid activation processing
3O
4And citric acid (nucleation control agent) mixes, and uses emulsification pretreatment stirrer high-speed stirring 15 minutes under the rotating speed of 4000r/min～6000r/min, still aging 6 hours, obtains Fe
3O
4Content is Attapulgite/Fe of 5wt%
3O
4Magnetic composite powder.
According to the proportioning in the raw material composition of polymeric amide/magnetic Attapulgite matrix material, with hexanolactam, magnetic Attapulgite composite granule, catalyzer and activator 120 ℃ of following vacuum hydro-extractions 90 minutes, being cast in preheating temperature rapidly and being 170 ℃ and intensity is in the mould of 80mT alternating magnetic field, react the demoulding after 20 minutes, obtain polymeric amide/magnetic Attapulgite matrix material.
Can prepare magnetic Attapulgite content according to the above ratio is 0.10wt% (gross weight with polymeric amide/magnetic Attapulgite matrix material is a base of calculation), Fe in the magnetic Attapulgite composite granule
3O
4Content is that 5wt% is (with Attapulgite/Fe
3O
4The gross weight of magnetic composite powder is a base of calculation).
Embodiment 2
1. pyroprocessing and acid activation processing montmorillonite suspension liquid prepares component (in parts by weight, letter meter " part " is down together):
(1) original montmorillonoid soil (400 order) is 100 parts
(2) sulfuric acid (10v/v%) is 10 parts
(3) dispersion agent is 3 parts
2. polynite/Fe
3O
4The magnetic composite powder raw material is formed:
(1) pyroprocessing and acid activation polynite are 100 parts
(2) ultra-fine Fe
3O
4(commercially available) 5 parts
(3) citric acid (nucleation control agent) is 1 part
3. the raw material of polymeric amide/magnetic montmorillonite composite material is formed:
(1) hexanolactam is 100 parts
(2) magnetic montmorillonite Composite powder is 0.10 part
(3) sodium is for 2.0 parts of hexanolactams
(4) TDI is 0.5 part
4. working method:
With original montmorillonoid soil 400 ℃ of pyroprocessing 2 hours in retort furnace, be cooled to that to add concentration after the room temperature be the sulfuric acid of 10v/v%, reacted 30 minutes, 100 ℃ activate 2 hours in baking oven, vacuum filtration obtains high-specific surface area polynite filter cake, being washed to the pH value is 7, oven dry is also pulverized, press high temperature and acid activation and handle the polynite powder, sodium polyacrylate (dispersion agent), quality is than being the mixed of 100:3:1000, uses emulsification pretreatment stirrer high-speed stirring 10 minutes under the rotating speed of 4000r/min～6000r/min, obtains pyroprocessing acid activation montmorillonite suspension liquid.
According to polynite/Fe
3O
4Proportioning during the magnetic composite powder raw material is formed will be through montmorillonite suspension liquid, the Fe of pyroprocessing and acid activation processing
3O
4Mix with nucleation control agent citric acid, use emulsification pretreatment stirrer high-speed stirring 15 minutes under the rotating speed of 4000r/min～6000r/min, still aging 6 hours, obtain Fe
3O
4Content is polynite/Fe of 5wt%
3O
4Magnetic composite powder.
According to the proportioning in the raw material composition of polymeric amide/magnetic montmorillonite composite material, with hexanolactam, magnetic montmorillonite Composite powder, catalyzer and activator 120 ℃ of following vacuum hydro-extractions 90 minutes, being cast in preheating temperature rapidly and being 170 ℃ and intensity is the mould of 80mT alternating magnetic field, react the demoulding after 20 minutes, obtain polymeric amide/magnetic montmorillonite composite material.
Can prepare magnetic polynite content according to the above ratio is 0.10wt% (gross weight with polymeric amide/magnetic Attapulgite matrix material is a base of calculation), Fe in the magnetic montmorillonite Composite powder
3O
4Content is that 5wt% is (with Attapulgite/Fe
3O
4The gross weight of magnetic composite powder is a base of calculation).
Embodiment 3
1. pyroprocessing and acid activation are handled Attapulgite suspension preparation component with embodiment 1.
2. Attapulgite/Fe
3O
4The magnetic composite powder raw material is formed:
(1) pyroprocessing and acid activation Attapulgite are 100 parts
(2) ultra-fine Fe
3O
4(commercially available) 10 parts
(3) nucleation control agent citric acid is 1 part
3. the raw material of polymeric amide/magnetic Attapulgite matrix material is formed:
(1) hexanolactam is 100 parts
(2) magnetic Attapulgite composite granule is 0.10 part
(3) sodium is for 2.0 parts of hexanolactams
(4) TDI is 0.5 part
4. working method:
Pyroprocessing and acid activation are handled Attapulgite suspension preparation method with embodiment 1, obtain pyroprocessing acid activation Attapulgite suspension.
According to Attapulgite/Fe
3O
4Proportioning during the magnetic composite powder raw material is formed, working method obtains Fe with embodiment 1
3O
4Content is Attapulgite/Fe of 10wt%
3O
4Magnetic composite powder.
According to the proportioning in the raw material composition of polymeric amide/magnetic Attapulgite matrix material, working method is with embodiment 1, can prepare the polymeric amide that magnetic Attapulgite content is 0.10wt%/magnetic Attapulgite matrix material (gross weight with polymeric amide/magnetic Attapulgite matrix material is a base of calculation), Fe in the magnetic Attapulgite composite granule
3O
4Content is 10wt% (Attapulgite/Fe
3O
4The gross weight of magnetic composite powder is a base of calculation).
Embodiment 4
1. pyroprocessing and acid activation processing montmorillonite suspension liquid prepares component with embodiment 2.
2. polynite/Fe
3O
4The magnetic composite powder raw material is formed:
(1) pyroprocessing and acid activation polynite are 100 parts
(2) ultra-fine Fe
3O
4(commercially available) 10 parts
(3) citric acid (nucleation control agent) is 1 part
3. the raw material of polymeric amide/magnetic montmorillonite composite material is formed:
(1) hexanolactam is 100 parts
(2) magnetic montmorillonite Composite powder is 0.10 part
(3) sodium is for 2.0 parts of hexanolactams
(4) TDI is 0.5 part
4. working method:
Pyroprocessing and acid activation are handled the montmorillonite suspension liquid preparation method with embodiment 2, obtain pyroprocessing acid activation montmorillonite suspension liquid.
According to polynite/Fe
3O
4Proportioning during the magnetic composite powder raw material is formed, working method obtains Fe with embodiment 2
3O
4Content is polynite/Fe of 10wt%
3O
4Magnetic composite powder.
According to the proportioning in the raw material composition of polymeric amide/magnetic montmorillonite composite material, working method is with embodiment 2, can prepare magnetic polynite content is 0.10wt% (gross weight with polymeric amide/magnetic Attapulgite matrix material is a base of calculation), Fe in the magnetic montmorillonite Composite powder
3O
4Content is that 10wt% is (with Attapulgite/Fe
3O
4The gross weight of magnetic composite powder is a base of calculation).
Embodiment 5
1. pyroprocessing and acid activation are handled Attapulgite suspension preparation component with embodiment 1.
2. Attapulgite/Fe
3O
4The magnetic composite powder raw material is formed:
(1) pyroprocessing and acid activation Attapulgite are 100 parts
(2) ultra-fine Fe
3O
4(commercially available) 5 parts
(3) citric acid (nucleation control agent) is 1 part
3. the raw material of polymeric amide/magnetic Attapulgite matrix material is formed:
(1) hexanolactam is 100 parts
(2) magnetic Attapulgite composite granule is 0.30 part
(3) sodium is for 2.0 parts of hexanolactams
(4) TDI is 0.5 part
4. working method:
Pyroprocessing and acid activation are handled Attapulgite suspension preparation method with embodiment 1, obtain pyroprocessing acid activation Attapulgite suspension.
According to Attapulgite/Fe
3O
4Proportioning during the magnetic composite powder raw material is formed, working method obtains Fe with embodiment 1
3O
4Content is Attapulgite/Fe of 5wt%
3O
4Magnetic composite powder.
According to the proportioning in the raw material composition of polymeric amide/magnetic Attapulgite matrix material, working method can prepare the polymeric amide that magnetic Attapulgite content is 0.30wt%/magnetic Attapulgite matrix material, Fe in the magnetic Attapulgite composite granule with embodiment 1
3O
4Content is 5wt%.
Embodiment 6
1. pyroprocessing and acid activation processing montmorillonite suspension liquid prepares component with embodiment 2.
2. polynite/Fe
3O
4The magnetic composite powder raw material is formed:
(1) pyroprocessing and acid activation polynite are 100 parts
(2) ultra-fine Fe
3O
4(commercially available) 5 parts
(3) nucleation control agent citric acid is 1 part
3. the raw material of polymeric amide/magnetic montmorillonite composite material is formed:
(1) hexanolactam is 100 parts
(2) magnetic montmorillonite Composite powder is 0.50 part
(3) sodium is for 2.0 parts of hexanolactams
(4) TDI is 0.5 part
4. working method:
Pyroprocessing and acid activation are handled the montmorillonite suspension liquid preparation method with embodiment 2, obtain pyroprocessing acid activation montmorillonite suspension liquid.
According to polynite/Fe
3O
4Proportioning during the magnetic composite powder raw material is formed, working method obtains Fe with embodiment 2
3O
4Content is polynite/Fe of 5wt%
3O
4Magnetic composite powder.
According to the proportioning in the raw material composition of polymeric amide/magnetic montmorillonite composite material, working method is with embodiment 2, can prepare magnetic polynite content is 0.50wt% (gross weight with polymeric amide/magnetic Attapulgite matrix material is a base of calculation), Fe in the magnetic montmorillonite Composite powder
3O
4Content is that 5wt% is (with Attapulgite/Fe
3O
4The gross weight of magnetic composite powder is a base of calculation).
Embodiment 7
1. pyroprocessing and acid activation processing Attapulgite/polynite mixing suspension prepares component:
(1) Attapulgite original soil (400 order) is 50 parts
(2) original montmorillonoid soil (400 order) is 50 parts
(3) sulfuric acid is (10%) 10 part
(4) dispersion agent is 3 parts
2. mixed clay/Fe
3O
4The magnetic composite powder raw material is formed:
(1) pyroprocessing and acid activation mixing suspension are 100 parts
(2) ultra-fine Fe
3O
4(commercially available) 5 parts
(3) nucleation control agent citric acid is 1 part
3. the raw material of polymeric amide/magnetic mixed clay matrix material is formed:
(1) hexanolactam is 100 parts
(2) magnetic mixed clay composite granule is 0.10 part
(3) sodium is for 2.0 parts of hexanolactams
(4) TDI is 0.5 part
4. working method:
With Attapulgite/polynite mixing original soil 400 ℃ of pyroprocessing 2 hours in retort furnace, be cooled to that to add concentration after the room temperature be 10% sulfuric acid, reacted 30 minutes, 100 ℃ activate 2 hours in baking oven, vacuum filtration obtains high-specific surface area mixed clay filter cake, being washed to the pH value is 7, oven dry is also pulverized, press high temperature and acid activation and handle mixed clay, dispersion agent, quality is than being the mixed of 100:3:1000, uses emulsification pretreatment stirrer high-speed stirring 10 minutes under the rotating speed of 4000r/min～6000r/min, obtains pyroprocessing acid activation mixed clay suspension.
According to mixed clay/Fe
3O
4Proportioning during the magnetic composite powder raw material is formed will be through mixed clay suspension, the Fe of pyroprocessing and acid activation processing
3O
4Mix with nucleation control agent citric acid, use emulsification pretreatment stirrer high-speed stirring 15 minutes under the rotating speed of 4000-6000r/min, still aging 6 hours, obtain Fe
3O
4Content is mixed clay/Fe of 5wt%
3O
4Magnetic composite powder.
According to the proportioning in the raw material composition of polymeric amide/magnetic mixed clay matrix material, with hexanolactam, magnetic mixed clay composite granule, catalyzer and activator 120 ℃ of following vacuum hydro-extractions 90 minutes, being cast in preheating temperature rapidly and being 170 ℃ and intensity is the mould of 80mT alternating magnetic field, react the demoulding after 20 minutes, obtain polymeric amide/magnetic mixed clay matrix material.
Can prepare magnetic mixed clay content according to the above ratio is 0.10wt% (gross weight with polymeric amide/magnetic Attapulgite matrix material is a base of calculation), Fe in the magnetic mixed clay composite granule
3O
4Content is that 5wt% is (with Attapulgite/Fe
3O
4The gross weight of magnetic composite powder is a base of calculation).
To the prepared polymeric amide/magnetic silicate clay matrix material of the foregoing description 1～7, carry out tensile property, impact property test respectively, the results are shown in Table 1.
Comparative Examples
Use the mixture modification nylon (polymeric amide) of Attapulgite, polynite or Attapulgite and polynite respectively, specific as follows:
Comparative Examples 1: divided by the magnetic Attapulgite composite granule in the Attapulgite alternate embodiment 5, and under no externally-applied magnetic field condition, carry out outside the in-situ polymerization, other condition and embodiment 5 just as, the matrix material of gained is noted by abridging and is: D1.
Comparative Examples 2: divided by the magnetic montmorillonite Composite powder in the polynite alternate embodiment 6, and under no externally-applied magnetic field condition, carry out outside the in-situ polymerization, other condition and embodiment 6 just as, the matrix material of gained is noted by abridging and is: D2.
Comparative Examples 3: divided by the magnetic mixed clay composite granule among the mixture replacing embodiment 7 of Attapulgite and polynite, and under no externally-applied magnetic field condition, carry out outside the in-situ polymerization, other condition and embodiment 7 just as, the matrix material of gained is noted by abridging and is: D3.Equally D1, D2 and D3 are carried out tensile property, impact property test respectively, the results are shown in Table 1.
Table 1
Claims (8)
1, a kind of magnetic silicate clay/polyamide compound resin, it is characterized in that, said magnetic silicate clay/polyamide compound resin is: having under catalyzer and the externally-applied magnetic field existence condition, mainly obtained behind in-situ polymerization by the acid amides of 100 parts by weight and the magnetic silicate clay of 0.05 parts by weight～0.10 parts by weight;
Wherein: said magnetic silicate clay is meant: load be magnetic sepiolite, polygorskite, polynite or the attapulgite of material; The magnetic substance charge capacity is: the magnetic substance of the sepiolite of 100 parts by weight, polygorskite, polynite or attapulgite load 5 parts by weight～10 parts by weight.
2, magnetic silicate clay/polyamide compound resin as claimed in claim 1 is characterized in that, wherein said acid amides is: hexanolactam.
3, magnetic silicate clay/polyamide compound resin as claimed in claim 2 is characterized in that, wherein used magnetic silicate clay is: the polynite of load Z 250 or attapulgite.
4, magnetic silicate clay/polyamide compound resin as claimed in claim 3 is characterized in that, wherein used catalyzer be sodium hydroxide or/and sodium for hexanolactam.
5, magnetic silicate clay/polyamide compound resin as claimed in claim 3 is characterized in that, has wherein also added activator, is mete-wand with the hexanolactam of 100 parts by weight, and the consumption of activator is 0.1 parts by weight～3 parts by weight.
6, magnetic silicate clay/polyamide compound resin as claimed in claim 5 is characterized in that, wherein said activator is that diphenylmethanediisocyanate is or/and tolylene diisocyanate.
As any described magnetic silicate clay/polyamide compound resin in the claim 3～6, it is characterized in that 7, wherein the in-situ polymerization temperature is 150 ℃～280 ℃, the in-situ polymerization time is 10 minutes～20 minutes.
8, magnetic silicate clay/polyamide compound resin as claimed in claim 7 is characterized in that, wherein the intensity of externally-applied magnetic field is 80mT～100mT.
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|---|---|---|---|
| CN2008102007279A CN101362858B (en) | 2008-09-28 | 2008-09-28 | Magnetic silicate clay/polyamide compound resin |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2008102007279A CN101362858B (en) | 2008-09-28 | 2008-09-28 | Magnetic silicate clay/polyamide compound resin |
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| CN101362858B CN101362858B (en) | 2010-09-01 |
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|---|---|---|---|
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102532523A (en) * | 2010-12-30 | 2012-07-04 | 上海杰事杰新材料(集团)股份有限公司 | Method for preparing magnetic polyamide composite material through in-situ hydrolysis |
| CN101760010B (en) * | 2008-12-26 | 2013-09-18 | 上海普利特复合材料股份有限公司 | Low odor and emission nylon 6 composition and preparation method thereof |
| CN103613922A (en) * | 2013-11-29 | 2014-03-05 | 江门市奇德工程塑料科技有限公司 | High-barrier nano PA6 composite material and preparation method thereof |
-
2008
- 2008-09-28 CN CN2008102007279A patent/CN101362858B/en not_active Expired - Fee Related
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101760010B (en) * | 2008-12-26 | 2013-09-18 | 上海普利特复合材料股份有限公司 | Low odor and emission nylon 6 composition and preparation method thereof |
| CN102532523A (en) * | 2010-12-30 | 2012-07-04 | 上海杰事杰新材料(集团)股份有限公司 | Method for preparing magnetic polyamide composite material through in-situ hydrolysis |
| CN102532523B (en) * | 2010-12-30 | 2014-09-10 | 上海杰事杰新材料(集团)股份有限公司 | Method for preparing magnetic polyamide composite material through in-situ hydrolysis |
| CN103613922A (en) * | 2013-11-29 | 2014-03-05 | 江门市奇德工程塑料科技有限公司 | High-barrier nano PA6 composite material and preparation method thereof |
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| Publication number | Publication date |
|---|---|
| CN101362858B (en) | 2010-09-01 |
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