CN102827318A - Polydicyclopentadiene building template material and its preparation method - Google Patents
Polydicyclopentadiene building template material and its preparation method Download PDFInfo
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- CN102827318A CN102827318A CN2011104549565A CN201110454956A CN102827318A CN 102827318 A CN102827318 A CN 102827318A CN 2011104549565 A CN2011104549565 A CN 2011104549565A CN 201110454956 A CN201110454956 A CN 201110454956A CN 102827318 A CN102827318 A CN 102827318A
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Abstract
The invention discloses a polydicyclopentadiene building template material. The polydicyclopentadiene building template material is obtained through blending polymerization of 80-99.99wt% of dicyclopentadiene and 0.01-20wt% of a glass fiber. The polydicyclopentadiene building template material selects the glass fiber as a reinforcement material to undergo blending polymerization with the dicyclopentadiene to synthesize the composite material, so the impact strength and the tensile strength of the polydicyclopentadiene material can be substantially improved only through adding a small amount of the glass fiber. The impact strength of the composite material is improved to 180-350J/m from original 100J/m of the single polydicyclopentadiene material, and the tensile strength of the composite material is improved to 30-35MPa from original 25MPa of the single polydicyclopentadiene material. The polydicyclopentadiene building template material enables building templates to be 1/6-1/7 lighter than templates prepared from steel, has the advantages of no rust generation, no deformation, and non-affinity with the building surface, and simultaneously overcomes the shortages of easy water absorption, easy mildewing, low strength and short service life of bamboo templates.
Description
Technical field
The present invention relates to a kind of polydicyclopentadiene building template material, relate to a kind of this preparation methods simultaneously.
Background technology
Building template is the important tool of concrete structure engineering construction.In the cast-in-place concrete structure engineering, form work engineering generally accounts for 20%～30% of concrete structure engineering cost, accounts for 30%～40% of the engineering amount of labour used, accounts for about 50% of the duration.Mould plate technique directly influences quality, cost and the benefit of engineering construction, so it is to promote important content of China's Building technology progressive.Along with Chinese economic development, Highrise buildings, high-rise building and large public building are built in a large number, large-scale infrastructure construction, and develop rapidlys such as Urban traffic and motorway, railway increase day by day to the building template demand.Annual building template usage quantity reached 5.85 hundred million square metres in 2009, and speedup is the speedup of maintenance about 10%% in 7.3%, 2010 year on year-on-year basis; The average annual industrial scale speedup of China's building template industry will be about 15% in 2011～2012.
The building template that uses at present generally has two kinds, and the one, steel template, the 2nd, bamboo wooden form.Steel template and cement have good affinity, and corrosion easily, so Sheet Steel Form demoulding difficulty after construction often must be done to cover one deck releasing agent before use, bring construction loaded down with trivial details; Releasing agent often also very easily pollutes reinforcing bar and building surface in addition, or causes quality accident or bring difficulty for next step building operation.Sheet Steel Form is prone in repeated use by collision deformation, and the very unfairness of the feasible cement surface that is poured often must be carried out smooth modification with cement once more.Take a lot of work, time-consuming, increase cost.The Sheet Steel Form of distortion is wanted frequent place under repair.The bamboo wooden form has strong absorptive, and the back weight of making moist increases, and after repeatedly using waterproof layer to be destroyed, causes bigger distortion, and intensity significantly reduces, and very easily damages.Simultaneously also can moldy metamorphism, damage the no utility value in back.
Occurred in recent years to be main plastic building template with the Vestolen PP 7052 caused people's attention because of advantages such as its light weight, corrosion resistant, the demoulding are easy.But large-area plastic mould is made difficulty, and cost is high, and rigidity is bad, thereby application also is restricted.
Summary of the invention
The purpose of this invention is to provide the high polydicyclopentadiene building template material of a kind of physical strength.
In order to realize above purpose, the technical scheme that the present invention adopted is: a kind of polydicyclopentadiene building template material is to be formed by following raw materials by weight percent blending polymerization: 80～99% NSC 7352s, 1～20% spun glass.
Said spun glass is surface oxidation modified glass-fiber or surperficial coupling modified glass-fiber.
The length of said spun glass is 1～12mm.
Polydicyclopentadiene building template material of the present invention adopts following method preparation:
1) 1～20% spun glass homogeneous in 80～99% liquid NSC 7352 is disperseed, obtain dispersion liquid;
2) dispersion liquid is divided into two parts, under protection of inert gas, in a part wherein, adds the aryloxy tungsten catalyst of NSC 7352 total mole number 1/1000～1/3000, stirring obtains A solution; Add the aluminum alkyls of 25～45 times of said tungsten catalyst mole numbers in another part, stirring obtains B solution;
3) under 40～90 ℃ of conditions with susceptible gas shield, A solution and the injection molding of B solution blending are obtained polydicyclopentadiene building template material.
Said spun glass is surface oxidation modified glass-fiber or surperficial coupling modified glass-fiber.
Wherein the surface oxidation modified glass-fiber can adopt following method preparation:
(1) spun glass being joined in 30% the superoxol, is to react 2～7 hours under 60～90 ℃ the condition in temperature;
(2) spun glass being changed in the concentrated nitric acid, is to react 3～6 hours under 100～120 ℃ the warm condition in temperature again;
(3) after reaction finishes the surface oxidation modified glass-fiber is taken out, being washed with distilled water to pH is 6～7, dries in the vacuum drying oven to constant weight and promptly gets the surface oxidation modified glass-fiber.
Wherein surperficial coupling differential fiber can adopt following method preparation:
(1) silane coupling agent being dissolved in organic solvent, to be made into massfraction be 10～20% solution, adds spun glass, said solution be spun glass quality 75-125 doubly; Adding Glacial acetic acid min. 99.5 then, to regulate the pH value be about 4～5, and with ultrasonic dispersing 5～6 hours, water temperature is controlled at carried out linked reaction about 60 ℃;
(2) after reaction finishes surperficial coupling modified glass-fiber is taken out, being washed with distilled water to pH is 6～7, dries in the vacuum drying oven to constant weight and promptly gets surperficial coupling modified glass-fiber.
The length of said spun glass is 1～12mm.
Said aryloxy tungsten catalyst is two (2,6 di-tert-butyls-4-methylphenoxy) tungsten tetrachloride.
Said aluminum alkyls is an aluminium diethyl monochloride.
Before the said injection of step 3) to mould and die preheating to 40-65 ℃, formpiston is higher 5～10 ℃ than former.
Step 3) said set time is 2～8 minutes.
Polydicyclopentadiene building template material of the present invention; Select spun glass to become matrix material with the NSC 7352 blending polymerization as strongthener; Only need to add shock strength and the tensile strength that a spot of spun glass just can improve dicyclopentadiene material significantly; Compare its shock strength of simple dicyclopentadiene material and bring up to 180～350J/m by original 100J/m, tensile strength is brought up to 30～35MPa by original 25MPa.
Material of the present invention is as building template, and is indeformable than the light sixth to seven of steel template/one, and non-corrosive, not affine with building surface, overcome simultaneously the bamboo wooden form easy suction, be prone to go mouldy, intensity is low and work-ing life section shortcoming.And the polydicyclopentadiene building template life-span is long, reuse often, can have enough to meet the need more than 50 times, and be 7 times of Bamboo Formworks, 16 times of wooden form.Comprehensive cost is 1/5～1/6 of a bamboo wooden form.
Polydicyclopentadiene building template material preparation method of the present invention in addition is simple to operate, easy to implement; Preparation efficiency is high; Wherein tungsten catalyst and aluminum alkyls adopt conventional bicomponent catalyst, i.e. aryloxy tungsten catalyst and aluminum alkyl catalyst, and the aryloxy tungsten catalyst preferred two (2 among the present invention; 6 di-tert-butyls-4-methylphenoxy) tungsten tetrachloride, the preferred aluminium diethyl monochloride of aluminum alkyls.
Embodiment
Below in conjunction with specific embodiment polydicyclopentadiene building template material of the present invention is carried out detailed explanation, but do not limit technical scheme of the present invention.The raw material NSC 7352, fiber precursor, tungsten catalyst, the aluminum alkyls that relate among the embodiment 1～5 are commercially available product.
Embodiment 1
The polydicyclopentadiene building template material of present embodiment is to be formed by following raw materials by weight percent blending polymerization: 98.5% polydicyclopentadiene and 1.5% spun glass, the length of spun glass are 10mm.
Polydicyclopentadiene building template preparation methods of the present invention may further comprise the steps:
(1) under 45 ℃ condition; To be 1.5% spun glass with weight percent be dispersed in weight percent through clarifixator is in 98.5% the NSC 7352; Obtain the homodisperse NSC 7352 mixing solutions of spun glass, the inflated with nitrogen protection is for use behind the vacuum pump degassing 25min;
(2) under nitrogen protection, in the A of reaction injection molding machine jar and B jar, add the homodisperse NSC 7352 mixed solution of 25 kg fiberglass respectively; In the A jar, add then 0.261 kilogram two (2,6 di-tert-butyls-4-methylphenoxy) tungsten tetrachloride (add-on be 49.25 kilograms the NSC 7352 mole number 1/1000); In the B jar, add 1.416 kilograms of aluminium diethyl monochlorides (be in the A jar tungsten catalyst mole number 35 times);
(3) temperature of charge in injection reaction shaper A, the B jar is remained on 70 ℃; Open two material recycle pumps of reaction injection molding machine simultaneously; The injection head of reaction injection molding machine is docked and opens filling gun with die orifice; Material in A, the B batch can injects mould (formpiston is higher 5 ℃ than the former) moulding of 60 ℃ of preheatings after the mixed at high speed in filling gun, heat preservation solidification die sinking in 2 minutes promptly obtains polydicyclopentadiene building template material.
The shock strength and the tensile strength of present embodiment material are seen shown in the table 1.
Embodiment 2
The polydicyclopentadiene building template material of present embodiment is to be formed by following raw materials by weight percent blending polymerization: 99.7% NSC 7352 and 0.3% spun glass, the length of spun glass are 1mm.
Polydicyclopentadiene building template preparation methods of the present invention may further comprise the steps:
(1) under 45 ℃ condition; To be 0.3% spun glass with weight percent be dispersed in weight percent through clarifixator is in 99.7% the NSC 7352; Obtain the homodisperse NSC 7352 mixing solutions of spun glass, the inflated with nitrogen protection is for use behind the vacuum pump degassing 25min;
(2) under nitrogen protection, in the A of reaction injection molding machine jar and B jar, add the homodisperse NSC 7352 mixing solutions of 25 kg fiberglass respectively respectively; In the A jar, add then 0.138 kilogram two (2,6 di-tert-butyls-4-methylphenoxy) tungsten tetrachloride (add-on be 49.85 kilograms the NSC 7352 mole number 1/1900); In the B jar, add 0.539 kilogram of aluminium diethyl monochloride (be in the A jar tungsten catalyst mole number 25 times);
(3) temperature of charge in injection reaction shaper A, the B jar is remained on 35 ℃; Under nitrogen protection, open two material recycle pumps of reaction injection molding machine simultaneously; The injection head of reaction injection molding machine is docked and opens filling gun with die orifice; Material in A, the B batch can injects mould (formpiston is higher 7 ℃ than the former) moulding of 40 ℃ of preheatings after the mixed at high speed in filling gun, heat preservation solidification die sinking in 5 minutes promptly obtains polydicyclopentadiene building template material.
The shock strength and the tensile strength of present embodiment material are seen shown in the table 1.
Embodiment 3
The polydicyclopentadiene building template material of present embodiment is made up of following components in weight percentage: the spun glass of 99% polydicyclopentadiene and 1% surperficial coupling modification, wherein the length of spun glass is 3mm.
Polydicyclopentadiene building template preparation methods of the present invention may further comprise the steps:
(1) 1 gram spun glass being added 75 gram mass marks is in 10% the KH-570 silane coupling agent acetone soln, and adding Glacial acetic acid min. 99.5, to regulate pH value be 4.5, and with ultrasonic dispersing reaction 5 hours, water temperature was controlled at 60 ℃ then; After reaction finishes surperficial coupling modified glass-fiber is taken out, being washed with distilled water to pH is 7, in 80 ℃ of following vacuum drying ovens, dries to constant weight and promptly gets surperficial coupling modified glass-fiber;
(2) under 45 ℃ condition; To be 1% surperficial coupling modified glass-fiber with mass percent be dispersed in mass percent through clarifixator is in 99% the NSC 7352; Obtain the homodisperse NSC 7352 mixing solutions of surperficial coupling modified glass-fiber, the inflated with nitrogen protection is for use behind the vacuum pump degassing 25min;
(3) under nitrogen protection, in the A of reaction injection molding machine jar and B jar, add 25 kilograms of homodisperse NSC 7352 mixed solutions of surperficial coupling modified glass-fiber respectively; In the A jar, add then 0.137 kilogram two (2,6 di-tert-butyls-4-methylphenoxy) tungsten tetrachloride (add-on be 49.5 kilograms the NSC 7352 mole number 1/1900); In the B jar, add 0.746 kilogram of aluminium diethyl monochloride (be in the A jar tungsten catalyst mole number 35 times);
(4) temperature of charge in injection reaction shaper A, the B jar is remained on 45 ℃; Open two material recycle pumps of reaction injection molding machine simultaneously; The injection head of reaction injection molding machine is docked and opens filling gun with die orifice; Material in A, the B batch can injects mould (formpiston is higher 10 ℃ than the former) moulding of 45 ℃ of preheatings after the mixed at high speed in filling gun, heat preservation solidification die sinking in 8 minutes promptly obtains polydicyclopentadiene building template material.
The shock strength and the tensile strength of present embodiment material are seen shown in the table 1.
Embodiment 4
The polydicyclopentadiene building template material of present embodiment is to be formed by following raw materials by weight percent blending polymerization: 99.99% polydicyclopentadiene and 0.01% spun glass, the length of spun glass are 7mm.
Polydicyclopentadiene building template preparation methods of the present invention may further comprise the steps:
(1) under 45 ℃ condition; To be 0.01% spun glass with weight percent be dispersed in weight percent through clarifixator is in 99.99% the NSC 7352; Obtain the homodisperse NSC 7352 mixing solutions of spun glass, the inflated with nitrogen protection is for use behind the vacuum pump degassing 25min.
(2) under nitrogen protection, in the A of reaction injection molding machine jar and B jar, add the homodisperse NSC 7352 mixed solution of 25 kg fiberglass respectively; In the A jar, add then 0.264 kilogram two (2,6 di-tert-butyls-4-methylphenoxy) tungsten tetrachloride (add-on be 49.995 kilograms the NSC 7352 mole number 1/1000); In the B jar, add 1.438 kilograms of aluminium diethyl monochlorides (be in the A jar tungsten catalyst mole number 35 times);
(3) temperature of charge in injection reaction shaper A, the B jar is remained on 70 ℃; Open two material recycle pumps of reaction injection molding machine simultaneously; The injection head of reaction injection molding machine is docked and opens filling gun with die orifice; Material in A, the B batch can injects mould (formpiston is higher 5 ℃ than the former) moulding of 60 ℃ of preheatings after the mixed at high speed in filling gun, heat preservation solidification die sinking in 6 minutes promptly obtains polydicyclopentadiene building template material.
The shock strength and the tensile strength of present embodiment material are seen shown in the table 1.
Embodiment 5
The polydicyclopentadiene building template material of present embodiment is made up of following components in weight percentage: 96% polydicyclopentadiene and 4% surface oxidation modified glass-fiber, wherein the length of spun glass is 12mm.
Polydicyclopentadiene building template preparation methods of the present invention may further comprise the steps:
(1) 1 gram spun glass being joined in 100 grams, 30% the superoxol, is reaction 5 hours under 80 ℃ the condition in temperature; Spun glass being changed in the concentrated nitric acid, is reaction 4 hours under 110 ℃ the warm condition in temperature again; After reaction finishes the surface oxidation modified glass-fiber is taken out, being washed with distilled water to pH is 7, in 80 ℃ vacuum drying oven, dries to constant weight and promptly gets the surface oxidation modified glass-fiber.
(2) under 45 ℃ condition; To be 2% surface oxidation modified glass-fiber with mass percent be dispersed in mass percent through clarifixator is in 98% the NSC 7352; Obtain the homodisperse NSC 7352 mixing solutions of surface oxidation modified glass-fiber, the inflated with nitrogen protection is for use behind the vacuum pump degassing 25min.
(3) under nitrogen protection, in the A of reaction injection molding machine jar and B jar, add 25 kilograms of homodisperse NSC 7352 mixed solutions of surface oxidation modified glass-fiber respectively; In the A jar, add then 0.133 kilogram two (2,6 di-tert-butyls-4-methylphenoxy) tungsten tetrachloride (add-on be 48 kilograms the NSC 7352 mole number 1/1900); In the B jar, add 0.622 kilogram of aluminium diethyl monochloride (be in the A jar tungsten catalyst mole number 30 times);
(4) temperature of charge in injection reaction shaper A, the B jar is remained on 60 ℃; Open two material recycle pumps of reaction injection molding machine simultaneously; The injection head of reaction injection molding machine is docked and opens filling gun with die orifice; Material in A, the B batch can injects mould (formpiston is higher 8 ℃ than the former) moulding of 55 ℃ of preheatings after the mixed at high speed in filling gun, heat preservation solidification die sinking in 4 minutes promptly obtains polydicyclopentadiene building template material.
The shock strength and the tensile strength of present embodiment material are seen shown in the table 1.
Embodiment 6
The polydicyclopentadiene building template material of present embodiment is to be formed by following raw materials by weight percent blending polymerization: 88% polydicyclopentadiene and 12% spun glass, the length of spun glass are 5mm.
Polydicyclopentadiene building template preparation methods of the present invention may further comprise the steps:
(1) under 45 ℃ condition; To be 12% spun glass with weight percent be dispersed in weight percent through clarifixator is in 88% the NSC 7352; Obtain the homodisperse NSC 7352 mixing solutions of spun glass, the inflated with nitrogen protection is for use behind the vacuum pump degassing 25min;
(2) under nitrogen protection, in the A of reaction injection molding machine jar and B jar, add the homodisperse NSC 7352 mixed solution of 25 kg fiberglass respectively; In the A jar, add then 0.122 kilogram two (2,6 di-tert-butyls-4-methylphenoxy) tungsten tetrachloride (add-on be 44 kilograms the NSC 7352 mole number 1/1900); In the B jar, add 0.761 kilogram of aluminium diethyl monochloride (be in the A jar tungsten catalyst mole number 40 times);
(3) temperature of charge in injection reaction shaper A, the B jar is remained on 70 ℃; Open two material recycle pumps of reaction injection molding machine simultaneously; The injection head of reaction injection molding machine is docked and opens filling gun with die orifice; Material in A, the B batch can injects mould (formpiston is higher 5 ℃ than the former) moulding of 60 ℃ of preheatings after the mixed at high speed in filling gun, heat preservation solidification die sinking in 10 minutes promptly obtains polydicyclopentadiene building template material.
The shock strength and the tensile strength of present embodiment material are seen shown in the table 1.
Embodiment 7
The polydicyclopentadiene building template material of present embodiment is to be formed by following raw materials by weight percent blending polymerization: 80% polydicyclopentadiene and 20% spun glass, the length of spun glass are 9mm.
Polydicyclopentadiene building template preparation methods of the present invention may further comprise the steps:
(1) under 45 ℃ condition; To be 20% spun glass with weight percent be dispersed in weight percent through clarifixator is in 80% the NSC 7352; Obtain the homodisperse NSC 7352 mixing solutions of spun glass, the inflated with nitrogen protection is for use behind the vacuum pump degassing 25min;
(2) under nitrogen protection, in the A of reaction injection molding machine jar and B jar, add the homodisperse NSC 7352 mixed solution of 25 kg fiberglass respectively; In the A jar, add then 0.07 kilogram two (2,6 di-tert-butyls-4-methylphenoxy) tungsten tetrachloride (add-on be 40 kilograms the NSC 7352 mole number 1/3000); In the B jar, add 0.493 kilogram of aluminium diethyl monochloride (be in the A jar tungsten catalyst mole number 45 times);
(3) temperature of charge in injection reaction shaper A, the B jar is remained on 50 ℃; Open two material recycle pumps of reaction injection molding machine simultaneously; The injection head of reaction injection molding machine is docked and opens filling gun with die orifice; Material in A, the B batch can injects mould (formpiston is higher 9 ℃ than the former) moulding of 50 ℃ of preheatings after the mixed at high speed in filling gun, heat preservation solidification die sinking in 8 minutes promptly obtains polydicyclopentadiene building template material.
The shock strength and the tensile strength of present embodiment material are seen shown in the table 1.
Experimental example
Polydicyclopentadiene building template material in the foregoing description 1～6 carries out tensile strength and impact strength test, and the test-results that obtains is as shown in table 1:
The tensile strength of table 1 embodiment 1～6 matrix material and impact strength test result
| Embodiment | 1 | 2 | 3 | 4 | 5 | 6 | 7 |
| Shock strength (J/m) | 176 | 246 | 287 | 196 | 312 | 341 | 186 |
| Tensile strength (MPa) | 29.3 | 32.5 | 33.2 | 31.6 | 33.7 | 34.2 | 29.8 |
Claims (10)
1. a polydicyclopentadiene building template material is characterized in that: be to be formed by following raw materials by weight percent blending polymerization: 80～99.99% NSC 7352s, 0.01～20% spun glass.
2. polydicyclopentadiene building template material according to claim 1 is characterized in that: said spun glass is surface oxidation modified glass-fiber or surperficial coupling modified glass-fiber.
3. polydicyclopentadiene building template material according to claim 1 is characterized in that: the length of said spun glass is 1～12mm.
4. polydicyclopentadiene building template preparation methods according to claim 1, it is characterized in that: its step is following:
1) 0.01～20% spun glass homogeneous in 80～99.99% liquid NSC 7352 is disperseed, obtain dispersion liquid;
2) dispersion liquid is divided into two parts, under protection of inert gas, in a part wherein, adds the aryloxy tungsten catalyst of NSC 7352 total mole number 1/1000～1/3000, stirring obtains A solution; Add the aluminum alkyls of 25～45 times of said tungsten catalyst mole numbers in another part, stirring obtains B solution;
3) under 35～70 ℃ of conditions with susceptible gas shield, with A solution and B solution blending be injected into moulding in the mold cavity, curing obtains polydicyclopentadiene building template material.
5. preparation method according to claim 4 is characterized in that: said spun glass is surface oxidation modified glass-fiber or surperficial coupling modified glass-fiber.
6. preparation method according to claim 4 is characterized in that: the length of said spun glass is 1～12mm.
7. preparation method according to claim 4 is characterized in that: said aryloxy tungsten catalyst is two (2,6 di-tert-butyls-4-methylphenoxy) tungsten tetrachloride.
8. preparation method according to claim 4 is characterized in that: said aluminum alkyls is an aluminium diethyl monochloride.
9. preparation method according to claim 4 is characterized in that: before the said injection of step 3) to mould and die preheating to 40-65 ℃, formpiston is higher 5～10 ℃ than former.
10. preparation method according to claim 4 is characterized in that: step 3) said set time is 2～8 minutes.
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| CN104448084A (en) * | 2014-11-29 | 2015-03-25 | 安徽丹凤集团桐城玻璃纤维有限公司 | Preparation process of glass fiber composite material |
| CN106905482A (en) * | 2015-12-23 | 2017-06-30 | 大连理工常熟研究院有限公司 | A kind of polymerizable composition, polymerizable composition and its composite and preparation method |
| CN113756565A (en) * | 2021-09-28 | 2021-12-07 | 北京怡泰盛达技术发展有限责任公司 | Special template mounting and dismounting system for building |
| CN113802828A (en) * | 2021-10-13 | 2021-12-17 | 北京怡泰盛达技术发展有限责任公司 | Anti-deformation system for reinforcing steel belt additionally arranged on special building template |
| CN115895160A (en) * | 2022-12-28 | 2023-04-04 | 东实汽车科技集团股份有限公司 | Polyester fiber reinforced polydicyclopentadiene composite material and preparation method thereof |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN113802828A (en) * | 2021-10-13 | 2021-12-17 | 北京怡泰盛达技术发展有限责任公司 | Anti-deformation system for reinforcing steel belt additionally arranged on special building template |
| CN115895160A (en) * | 2022-12-28 | 2023-04-04 | 东实汽车科技集团股份有限公司 | Polyester fiber reinforced polydicyclopentadiene composite material and preparation method thereof |
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Application publication date: 20121219 |