CN102153710A

CN102153710A - Preparation method of modified petroleum resin

Info

Publication number: CN102153710A
Application number: CN 201110116550
Authority: CN
Inventors: 徐力群; 彭文平
Original assignee: SHANGYU JAVA MACROMOLECULE MATERIAL CO Ltd
Current assignee: Zhejiang Java Specialty Chemicals Co ltd
Priority date: 2011-05-06
Filing date: 2011-05-06
Publication date: 2011-08-17
Anticipated expiration: 2031-05-06
Also published as: CN102153710B

Abstract

本发明公开了一种马来酸酐接枝石油树脂的制备方法，属于有机高分子领域，用于解决木塑复合材料中相容性差的问题。其技术方案是：将石油树脂、马来酸酐升温溶解，在100～200℃之间滴加引发剂，滴加时间为0.5～1h，滴加完成后反应0.5～4h，然后在真空状态下抽提出剩余的马来酸酐，得到改性石油树脂产物。此产物用于木塑复合材料中，能显著提高木粉在塑料基体中的分散，从而提高木塑复合材料的力学性能，得到性能优异的木塑复合材料。The invention discloses a preparation method of maleic anhydride grafted petroleum resin, which belongs to the field of organic polymers and is used for solving the problem of poor compatibility in wood-plastic composite materials. Its technical scheme is: dissolve petroleum resin and maleic anhydride at high temperature, add the initiator dropwise at 100-200°C, the dropping time is 0.5-1h, react for 0.5-4h after the dropping is completed, and then pump it under vacuum. The remaining maleic anhydride is extracted to obtain a modified petroleum resin product. This product is used in wood-plastic composite materials, which can significantly improve the dispersion of wood powder in the plastic matrix, thereby improving the mechanical properties of wood-plastic composite materials, and obtaining wood-plastic composite materials with excellent performance.

Description

A kind of preparation method of modified petroleum resin

Technical field

The invention belongs to the organic polymer field, be specifically related to the preparation method of petroleum resin grafted maleic anhydride, and the application in wood plastic composite.

Background technology

Wood plastic composite is owing to be raw material with rejected materials such as waste plastic, wood chip, stalks, have energy-conserving and environment-protective, intensity height, not fugitive color, anti-ly damage by worms, outstanding advantage such as corrosion resistance and good, have work-ing life and anti-aging function than the multiplication of goods such as pure plastics and anticorrosion wood, become the good substitute products of plastics and anticorrosion woodwork, extensively be used as various occasions such as exterior decoration, Garden Engineering construction, workshop antiseptic project, ocean antiseptic project, environment sanitation facility, caused showing great attention to of various countries investigators in recent years.Although wood plastic composite has plurality of advantages, but because polarity, the plastics of wood powder nonpolar in the wood plastic composite, make that both consistencies are poor, the compatilizer that uses at present has titanic acid ester, aluminic acid ester, silane coupling agent, maleic anhydride graft polyolefine etc. in the industry.Certain effect has been played in the use of these compatilizers, but effect is undesirable, and it is relatively poor to show as mechanical property, and water-intake rate is high, and the application on exterior decoration, Garden Engineering construction, ocean antiseptic project is subjected to very big restriction like this.Therefore, the compatilizer of seeking a kind of better performances is the focus of paying close attention in the industry always.

Petroleum resin are that by product C5, the C9 cut with ethylene unit is main raw material, the low relative molecular mass polymkeric substance of the solid-state or thick liquid state that polymerization makes.At present, the petroleum resin of petroleum resin and modification thereof the petroleum resin that have been widely used in industries, particularly modified by maleic acid anhydride graft such as printing ink, papermaking, coating, rubber are applied in existing report in paper glue paste, the marking lines lacquer.Application number CN200810048398.0 discloses a kind of modified petroleum resin sizing agent that is used for paper sizing, is the mixture of compositions such as modified petroleum resin, dispersion agent, retention filtration adjuvant; Application number CN200410084024.6 discloses a kind of C ₉The preparation method of-copolymer-maleic anhydride is mainly used in Scale inhibitors etc.All there are the low characteristics of percentage of grafting in these modified petroleum resins, therefore, can't be used in the wood plastic composite.

Summary of the invention

For reaching, the problem that solves wood plastic composite consistency difference rationally utilizes petroleum resin, the present invention is by improving the maleic anhydride graft preparation method of petroleum resin, improve its percentage of grafting, be applied in the wood plastic composite, the result surprisingly, can obviously improve wood plastic composite mechanical property, thereby obtain the matrix material of excellent performance.

Patent of the present invention solves the technical scheme that its technical problem adopts:

1) raw materials pretreatment: with petroleum resin 170～200 ℃ ,-0.08～-pressure of 0.1Mpa under underpressure distillation 0.5～2h, remove the low cut in the petroleum resin;

2) polyreaction: the petroleum resin that pre-treatment is good cool to 100～150 ℃, add that to account for total reactant quality per-cent be 3～25% maleic anhydride, be warmed up between 100～200 ℃ and drip that to account for total reactant quality per-cent be 0.1～1% initiator, the dropping time is 0.5～1h, be added dropwise to complete afterreaction 0.5～4h, obtain polymer fluid;

3) removing of maleic anhydride and low cut: after reaction finishes, be warming up to 170～200 ℃ ,-0.08～-pressure of 0.1Mpa under underpressure distillation go out unnecessary maleic anhydride and low cut, obtain modified resin product.

Wherein, described petroleum resin comprise C5 petroleum resin, C9 petroleum resin, C5 and C9 copolymerized petroleum resin, and preferred bromine number is between 10～90gBr/100g, between preferred especially 20～50gBr/100g.

Described initiator is a peroxide initiator, as benzoyl peroxide, dicumyl peroxide, di-t-butyl peroxide, tert-butyl peroxide etc.

Contrast prior art according to the present invention following advantage arranged:

1, grafted method of the present invention adopts solventless method, therefore, and safety and environmental protection economy.

2, the present invention has carried out pre-treatment to raw material, has removed the lower-molecular substance that influences percentage of grafting, thereby has improved percentage of grafting.

3, the present invention has carried out removing of maleic anhydride at last, and last maleic anhydride residual in product is few, and therefore the basic odorlessness of product, has improved the Working environment of product when using.

According to technology of the present invention, obtain higher percentage of grafting product, be applied in the PE wood plastic composite, can obviously improve the mechanical property of wood plastic composite, thereby obtain the Wood model compound products of excellent performance.

Embodiment

Embodiment 1

In flask, add 200g C 5 petroleum resin (bromine number is 40gBr/100g) intensification fusion, and be warming up to 180～190 ℃, in-0.08～-vacuum pressure of 0.1Mpa under underpressure distillation 1h.Cool to 120～130 ℃ then, add the 30g maleic anhydride, be warmed up to 135～145 ℃ after the dissolving, in 0.5～1h, drip the 2g dicumyl peroxide, be added dropwise to complete afterreaction 2h, after reaction is finished, be warming up to 170～200 ℃,-0.08～-remove maleic anhydride and catalyzer under the 0.1Mpa vacuum pressure, obtain the C 5 modified petroleum resin product.Detecting its percentage of grafting is 11.2%.

Embodiment 2

In flask, add 200g C 9 petroleum resin (bromine number is 45gBr/100g) intensification fusion, and be warming up to 180～190 ℃, in-0.08～-vacuum pressure of 0.1Mpa under underpressure distillation 1h.Cool to 120～130 ℃ then, add the 25g maleic anhydride, be warmed up to 145～155 ℃ after the dissolving, two (tert-butyl hydroperoxide sec.-propyl) benzene of slow 2g in 0.5～1h, add afterreaction 3h, reaction is finished, and is warming up to 170～200 ℃,-0.08～-remove maleic anhydride and catalyzer under the 0.098Mpa vacuum pressure, obtain carbon nine modified petroleum resin products.Detecting its percentage of grafting is 10%.

Embodiment 3

In flask, add 200g carbon five, carbon nine copolymerized petroleum resins (bromine number is 30gBr/100g) intensification fusion, and be warming up to 180～190 ℃, in-0.08～-vacuum pressure of 0.1Mpa under underpressure distillation 1h.Cool to 120～130 ℃ then, add the 30g maleic anhydride, be warmed up to 145～155 ℃ after the dissolving, two (tert-butyl hydroperoxide sec.-propyl) benzene of slow 2g in 0.5～1h, add afterreaction 3h, reaction is finished, and is warming up to 170～200 ℃,-0.08～-remove maleic anhydride and catalyzer under the 0.098Mpa vacuum pressure, obtain the modified copolymer petroleum resin products.Detecting its percentage of grafting is 8%.

The testing method that above-mentioned percentage of grafting adopts is:

(1) grafts is refining

Take by weighing about 10g modified petroleum resin product, add 40ml dimethylbenzene, temperature rising reflux 0.5h all dissolves to sample, and the cooling back added the 400ml acetone precipitation 1 hour, filtered, and filter cake is put into 100 ℃ oven drying 10h, cooling.

(2) mensuration of maleic anhydride content

Take by weighing about 2g purified product, place the 250ml matrass, add 80ml dimethylbenzene, heating for dissolving, the cooling back adds excessive 0.1mol/L KOH-ethanol standardized solution, reheat backflow 6h, the cooling back is an indicator with phenolphthalein, instead drip excessive KOH one ethanol standardized solution with 0.1mol/L HC1 one Virahol standardized solution, write down excessive alkali number that consumes and neutral acid amount, calculate percentage of grafting.

Modified petroleum resin product and sec.-propyl three (dioctylphyrophosphoric acid acyloxy) titanic acid ester (Comparative Examples 1), maleic anhydride grafted polyethylene (Comparative Examples 2) that the foregoing description is obtained are applied in the PE wood plastic composite, concrete Application Example 1.

Application Example 1

With wood powder (100 order), HDPE, compatilizer in wood powder: HDPE: ratio premix 10min in high-speed mixer of compatilizer=50: 50: 1, then in twin screw extruder, under 150～160 ℃, melt extrude, the granulation oven dry, after using thermocompressor hot-forming then, detect its tensile strength, flexural strength, shock strength, detected result is as follows:

	Tensile strength (MPa)	Shock strength (KJ/m ²)	Flexural strength (MPa)
				Embodiment 1	38	4.8	50
Embodiment 2	35	4.6	48
				Embodiment 3	37	4.7	52
Comparative Examples 1	28	3.5	45
				Comparative Examples 2	29	4	44

Claims

1. a preparation method of modified petroleum resin, is characterized in that, comprises the steps:

(1) Raw material pretreatment: Distill the petroleum resin under reduced pressure at 170-200°C and -0.08-0.1Mpa for 0.5-2 hours to remove low fractions in the petroleum resin;

(2) Polymerization reaction: cool the pretreated petroleum resin to 100-150°C, add maleic anhydride with a mass percentage of 3-25% of the total reactant, and add dropwise to the total reaction mass percentage between 100-200°C Initiator whose substance mass percentage is 0.1-1%, the dropping time is 0.5-1h, after the dropping is completed, react for 0.5-4h to obtain the polymerization solution;

(3) Removal of maleic anhydride and low fractions: After the reaction is completed, heat up to 170-200°C, and distill excess maleic anhydride and low fractions under reduced pressure under the pressure of -0.08-0.1Mpa to obtain modified Resin products.

2. the preparation method of modified petroleum resin according to claim 1 is characterized in that described petroleum resin is C5 petroleum resin, C9 petroleum resin or C5 and C9 copolymerized petroleum resin.

3. The preparation method of modified petroleum resin according to claim 2, characterized in that the bromine value of petroleum resin is between 10～90gBr/100g, preferably between 20～50gBr/100g.

4. the preparation method of modified petroleum resin according to claim 1 is characterized in that described initiator is a peroxide initiator, such as benzoyl peroxide, dicumyl peroxide, di-tert-peroxide Butyl, or tert-butyl peroxide.

5. the application of the modified petroleum resin claimed in claim 1 in wood-plastic composite materials.

6. The wood-plastic composite material according to claim 5 is PE wood-plastic composite material.